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C3-Symmetric Nonadentate Ligand Systems Bearing Both Pyridine and Diamide Moieties for the Extraction of Lanthanides and...

Permanent Link: http://ufdc.ufl.edu/UFE0021413/00001

Material Information

Title: C3-Symmetric Nonadentate Ligand Systems Bearing Both Pyridine and Diamide Moieties for the Extraction of Lanthanides and Actinides and DFT Level Computational Studies for the Molecular Orbitals and Electronic Transitions of Expanded Porphyrin Systems Bearing Bis(Naphtoazuleneone) Ring Systems
Physical Description: 1 online resource (166 p.)
Language: english
Creator: Ozbek, Ozge
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2007

Subjects

Subjects / Keywords: actinides, azuleneone, dft, diamide, dicarboxyamide, expanded, extraction, lanthanides, ligand, naphtoazuleneone, nuclear, orbitals, porphyrin, pyridine, separation, triphenoxymethane, trivalent, waste
Chemistry -- Dissertations, Academic -- UF
Genre: Chemistry thesis, Ph.D.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Abstract: Separation of radioactive actinides from lanthanides in nuclear waste is important since transmutation of actinides in the presence of lanthanides is impossible. Nonadente ligands were synthesized with the introduction of unsymmetrical pyridine-2, 6-dicarboxamide groups to the preorganizing triphenoxymethane platform. The new incenerable ligand systems have the advantage of combining both the pyridine and diamide groups on one platform to work cooperatively for the extraction of trivalent metals from acid solutions. Ligand systems with two different types of triphenoxymethane platforms, lower side functionalized triphenoxymethane platform and upper side functionalized triphenoxymethane platform, have been synthesized. The results of the extraction experiments with trivalent lanthanides in 1 M nitric acid solutions reveal that all the ligand systems show moderate extraction of lanthanides by themselves but when the synergist COSAN is used, enhanced extraction behaviors are observed with lower side functionalized ligands except with the ligand with octyl protected platform with isopropyl groups as substituents. The results indicate that the solubility of the complexes forming during the extractions and the relative concentrations of the synergist COSAN, the extraction ligand and the metal play major role for the extraction behaviours of the ligands. Also, solid state structures of the complexes with upper side functionalized ligand with Tm and Yb indicate the geometry around metal is tricapped trigonal prism as expected for the metal complex with lanthanide (III) ions. The synthesis of the ligands and the results of the extraction experiments are discussed herein. The efficiencies of the ligands are compared. The electronic properties of the expanded porphyrin systems, cis- and trans-azuleneone derivatives, were of interest and computational studies of these molecules have been performed at DFT level. Excited state calculations were performed with TDDFT. The calculated and experimental geometries for the cis- isomer were compared and the results were determined to be in good agreement. Calculated excited states for each of the molecules were also consistent with the experimental spectra of the molecules. Detailed analysis of the calculated orbitals, orbital energies and both the experimental and the calculated spectra of the molecules revealed that the cis- isomer has split Q band region due to electronic affects of the substituents and symmetry lowering. Also the B-band regions of both of the molecules show contributions coming from lower lying orbitals. Both the experimental and theoretical results reveal that both of the molecules are red shifted due to ?- conjugation. All the details of the analysis and comparisons of the calculated and experimental data are discussed herein.
General Note: In the series University of Florida Digital Collections.
General Note: Includes vita.
Bibliography: Includes bibliographical references.
Source of Description: Description based on online resource; title from PDF title page.
Source of Description: This bibliographic record is available under the Creative Commons CC0 public domain dedication. The University of Florida Libraries, as creator of this bibliographic record, has waived all rights to it worldwide under copyright law, including all related and neighboring rights, to the extent allowed by law.
Statement of Responsibility: by Ozge Ozbek.
Thesis: Thesis (Ph.D.)--University of Florida, 2007.
Local: Adviser: Scott, Michael J.

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2007
System ID: UFE0021413:00001

Permanent Link: http://ufdc.ufl.edu/UFE0021413/00001

Material Information

Title: C3-Symmetric Nonadentate Ligand Systems Bearing Both Pyridine and Diamide Moieties for the Extraction of Lanthanides and Actinides and DFT Level Computational Studies for the Molecular Orbitals and Electronic Transitions of Expanded Porphyrin Systems Bearing Bis(Naphtoazuleneone) Ring Systems
Physical Description: 1 online resource (166 p.)
Language: english
Creator: Ozbek, Ozge
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2007

Subjects

Subjects / Keywords: actinides, azuleneone, dft, diamide, dicarboxyamide, expanded, extraction, lanthanides, ligand, naphtoazuleneone, nuclear, orbitals, porphyrin, pyridine, separation, triphenoxymethane, trivalent, waste
Chemistry -- Dissertations, Academic -- UF
Genre: Chemistry thesis, Ph.D.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Abstract: Separation of radioactive actinides from lanthanides in nuclear waste is important since transmutation of actinides in the presence of lanthanides is impossible. Nonadente ligands were synthesized with the introduction of unsymmetrical pyridine-2, 6-dicarboxamide groups to the preorganizing triphenoxymethane platform. The new incenerable ligand systems have the advantage of combining both the pyridine and diamide groups on one platform to work cooperatively for the extraction of trivalent metals from acid solutions. Ligand systems with two different types of triphenoxymethane platforms, lower side functionalized triphenoxymethane platform and upper side functionalized triphenoxymethane platform, have been synthesized. The results of the extraction experiments with trivalent lanthanides in 1 M nitric acid solutions reveal that all the ligand systems show moderate extraction of lanthanides by themselves but when the synergist COSAN is used, enhanced extraction behaviors are observed with lower side functionalized ligands except with the ligand with octyl protected platform with isopropyl groups as substituents. The results indicate that the solubility of the complexes forming during the extractions and the relative concentrations of the synergist COSAN, the extraction ligand and the metal play major role for the extraction behaviours of the ligands. Also, solid state structures of the complexes with upper side functionalized ligand with Tm and Yb indicate the geometry around metal is tricapped trigonal prism as expected for the metal complex with lanthanide (III) ions. The synthesis of the ligands and the results of the extraction experiments are discussed herein. The efficiencies of the ligands are compared. The electronic properties of the expanded porphyrin systems, cis- and trans-azuleneone derivatives, were of interest and computational studies of these molecules have been performed at DFT level. Excited state calculations were performed with TDDFT. The calculated and experimental geometries for the cis- isomer were compared and the results were determined to be in good agreement. Calculated excited states for each of the molecules were also consistent with the experimental spectra of the molecules. Detailed analysis of the calculated orbitals, orbital energies and both the experimental and the calculated spectra of the molecules revealed that the cis- isomer has split Q band region due to electronic affects of the substituents and symmetry lowering. Also the B-band regions of both of the molecules show contributions coming from lower lying orbitals. Both the experimental and theoretical results reveal that both of the molecules are red shifted due to ?- conjugation. All the details of the analysis and comparisons of the calculated and experimental data are discussed herein.
General Note: In the series University of Florida Digital Collections.
General Note: Includes vita.
Bibliography: Includes bibliographical references.
Source of Description: Description based on online resource; title from PDF title page.
Source of Description: This bibliographic record is available under the Creative Commons CC0 public domain dedication. The University of Florida Libraries, as creator of this bibliographic record, has waived all rights to it worldwide under copyright law, including all related and neighboring rights, to the extent allowed by law.
Statement of Responsibility: by Ozge Ozbek.
Thesis: Thesis (Ph.D.)--University of Florida, 2007.
Local: Adviser: Scott, Michael J.

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2007
System ID: UFE0021413:00001


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C3-SYMMETRIC NONADENTATE LIGAND SYSTEMS BEARING BOTH PYRIDINE AND
DIAMIDE MOIETIES FOR THE EXTRACTION OF LANTHANIDES AND ACTINIDES
AND DFT LEVEL COMPUTATIONAL STUDIES FOR THE MOLECULAR ORBITALS
AND ELECTRONIC TRANSITIONS OF EXPANDED PORPHYRIN SYSTEMS BEARING
BIS(NAPHTOAZULE~NEONE RING SYSTEMS

















By

OZGE OZBEK


A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY

UNIVERSITY OF FLORIDA

2007
































O 2007 Ozge Ozbek


































To my mom and dad









ACKNOWLEDGMENTS

First I would like to express my thanks to my research advisor Dr. Michael. J. Scott for

valuable discussion and mentoring in chemistry. His enthusiasm for chemistry and his guidance

made this study a successful one. I did learn a lot of chemistry during my studies and I am

thankful for this to Dr. Scott. I also want to express my appreciation for him for being a

responsible advisor and taking the full responsibility of his job. Today I am receiving my degree

because he takes his responsibilities seriously. That is something I am going to appreciate for the

rest of my life.

I would have never made it to this point without Dr. Adrian E. Roitberg. I have a lot of

things to thank him for. First of all he helped me to make my dream come true. He taught me

computational chemistry starting from beginner' s level with a great patience. The more I wanted

to learn, the more he taught me. Moreover he always supported me and encouraged me to go on

my way and most importantly he always appreciated and respected the work I was doing. In

addition to his support for my research studies, he also supported me psychologically. Actually

both Dr. Valeria D. Kleiman and Dr. Roitberg supported and helped me a lot so that I made them

my Argentinean parents here. I will always appreciate their help and believing in me for the rest

of my life. The most important and the most appreciable thing about Dr. Roitberg helping me

with my computational studies is that he himself volunteered to help me. It was very nice of him

and I want to thank him for doing this favor for me.

I want to express my thanks to Dr. Daniel R. Talham and Dr. David E. Richardson for their

endless support and their help for me. Their help, support and encouragement mean a lot to me

and I will never forget it.

One of the most important moments for me was the first moment I came to the Chemistry

Department. It was Dr. James A. Deyrup's very nice, friendly and warm welcome which made it










so special and unforgettable. He also helped me a lot for a lot of things until he got retired. I am

very much thankful to him for everything.

I am also grateful to Dr. Ben W. Smith. Whenever I needed him he was always there to

help me and to support me. I appreciate him for all his help, support and his great understanding.

One of the people who helped me a lot is Lori Clark. She has always been a great life saver

and a great friend. She actually became my American Mom and took really good care of me. I

appreciate her help, support and friendship a lot.

Here in UF I have met extremely nice people and had the honor of getting friends with

them. All of them are very special for me, deeply in my heart. Actually I prefer to call them as

family rather than friends. We, altogether, shared a lot together. We shared our happiness, our

unhappiness, good times, bad times and each moment made us come closer to each other and at

the end we became a huge family. I want to thank all of them for sharing their good heart with

me. I want to start thanking from Sarah M. Lane. She is my very first friend and my very

appreciable support. She has done all the nicest things ever possible for me for five years. She

has a very big heart, which I call diamond heart, and I am so happy to have her as my friend.

Another very close friend with a lot of love, help and support with a big heart is Laurel Reitfort.

Her enthusiasm of life has always cheered me up here. They both showed great hospitality with

very warm feelings. There is a very sweet couple that I want to thank for becoming my family;

Fedra Leonik and Daniel Kuroda. They are very thoughtful, caring, helpful, nice, and full of

love. They both do have a very big heart to share. I am grateful to them for all the nice things

they have done for me. Another member of my huge family is Melanie Veige. I will always

remember her with the colorful flowers that she gave me from her garden. She is super nice,

thoughtful, helpful and supportive. I am so glad to be friends with such a person with nothing but









goodness in her heart. Also it was a great pleasure for me to discuss chemistry with her as well.

There is another couple that I enj oy sharing a true family relation: Dr. Ranj an Mitra and Rashmi

Bagai. They are definitely a family for me. Ranj an is like a protecting brother to me. He has been

patient enough to answer all the questions I ask and he taught me a lot of stuff in the lab. He was

always helpful and full of support and a great brother. Rashmi has always been like a sister to me

with her kind, thoughtful, warm loving heart. I shared a lot with her and am glad to have both

Ranj an and her in my life as a family. Another big support for me is Sinan Selguk. He is super

nice, friendly and full of support. I do not think I could have survived here without him.

I also thank to Scott Group members. It was a pleasure to work with Dr. Ivana Bozideravic

and Dr. Hubert Gill. We had great discussions with Dr. Gill on porphyrin systems. I also want to

thank Dr. Elon Ison for all his help for the computational studies. He was a great person, a great

friend and a big support. Also I am grateful to Dr. Ajah Sah and Dr. Priya Srinivasan for their

help and friendships. I also want to thank Candace Zieleniuk and Eric Libra for being very nice

lab mates for four years. I appreciate all their help.

Many thanks need to go all the way to Turkey as well. I want to thank to the two

professors I worked years ago who have been supporting me with their emails. I am grateful to

Dr. Hiiseyin ISgi and Dr. Ahmet M. Ojnal. They always believed in me and they always told me

to go on. I will always appreciate their support and cheering me up with their emails.

Lastly and most importantly I want to thank to the most precious people in my heart; my

mom Betiil Ojzbek, and my dad, Nihat Ojzbek. They make my life a fairy tale. I couldn't have

wished for a better family. I consider myself the luckiest person in the world to have such a

family. There is nothing important as much as my family. No matter how tough life is, as long as

I feel their love I feel I can do anything in life. I do not know how to thank them for being such a










family to me. Even if I bought all the flowers and all the gifts for them, it wouldn't be enough

how much I am thankful to them and how much I love them. I have one last thing to say to my

parents: I love you, mom and I love you, dad .. and nothing else matters.

Chairman's Comments

Inorganic chemistry is a very large field to work in. It has a lot of applications in industry

as well as in academic research. The field of inorganic chemistry is closely related to physical

chemistry, organic chemistry, biochemistry and industrial chemistry. The reason it is related to

these other fields of application of chemistry is that the main interests of inorganic chemists are

the transition metals, reaction kinetics, spectroscopy and the molecular orbital approach to be

able to understand experimental results from the point of theory. A lot of biological reactions

take place in a cell and transition metals and their complexes are involved in these reactions as

biological catalysts. Moreover a lot of transition metals are used for pharmacologic research to

develop new medicines. The most famous of this application is the cis platinum complex that is

being used for cancer drugs and its derivatives are under study by bioinorganic chemists to

further develop more effective medicine for cancer.

On the other hand there is a big contribution of inorganic chemistry to the industry. A lot

of processes that involve chemical reactions in industry need transition metals and their

complexes for the catalysis of these reactions to occur in the fastest way, and the most economic

way. That is why a lot of catalysis research is going on to develop new catalysts for industrial

purposes.

Another interest of inorganic chemistry is the spectroscopy. Approaching spectroscopy

with respect to theory is of great interest. Transition metals or some of the ligands that transition

metals make complexes with show very interesting spectroscopic properties. Therefore their

spectroscopic behaviors are extensively studied and the reason of the transitions taking place in










the spectra of these molecules is explained with the molecular orbital approach which is

commonly used in inorganic chemistry to provide an explanation theoretically.

As a result of being in a wide area of a research field, we were interested in both the

industrial application of inorganic chemistry and the spectroscopic studies.

Our research from the side of industrial application of inorganic chemistry was to do

research to develop a new, efficient ligand system to react with lanthanide and actinide cations

selectively to be able to separate them from each other. This is a very important task because

every day in nuclear reactors a lot of radioactive waste is generated. These wastes are extremely

harmful for the environment and the human health but unfortunately it can not be converted into

a short term waste or less harmful waste since the process to achieve this goal goes through the

selective separation of these chemically very similar metal ions from each other. A lot of

research around the world is being done to solve this problem. Therefore we prepared a new

ligand system and tried to see if it is going to be efficient for the industrial application. The half

of this document involves the research on these ligand systems for the nuclear waste

management.

We were also interested in the spectroscopic properties of the porphyrin systems. These

systems are biologically important systems especially with their presence in hemoglobin. In

addition to important biological activities of these molecules, they show every interesting

spectroscopic properties. Wide research has been going on with the spectroscopic properties of

these molecules. Gouterman developed a theoretical explanation for the spectroscopic

characteristics of these molecules from molecular orbital approach. Although a lot of

spectroscopic research has been done with the simple porphyrin systems, there is not too many

with large porphyrin systems. In order to see how the substituents affect the spectroscopic










properties of these molecules, in our lab large porphyrin molecules called Azuleneones were

synthesized and experimental studies for the electronic spectroscopy of these molecules were

performed. In order to be able to understand the interesting spectroscopic behaviors of these

molecules we focused on working on these molecules from theoretical approach and be able to

explain the electronic transitions taking place with respect to theory. The second half of this

work is the detailed study of the theoretical studies of these porphyrin derivatives.

In conclusion, this document combines more than one application of inorganic chemistry

in detail: industrial and theoretical application. Details of the results are presented herein.











TABLE OF CONTENTS


page

ACKNOWLEDGMENT S .............. ...............4.....


CHAIRMAN' S COMMENTS S................ .................................... ...............7

LIST OF TABLES ................ ...............13........... ....


LIST OF FIGURES .............. ...............15....

LIST OF SCHEMES ................. ...............19.......... ..


AB S TRAC T ......_ ................. ............_........2

CHAPTER


1 INTRODUCTION ................. ...............22.......... ......

1.1 Nuclear W aste .................. ........... ...... ....... ... .. .. .........2
1.2 Nuclear Incineration of Trans-Uranium Actinides: Transmutation ................... ...........23
1.3 Chemical Properties of Lanthanides and Actinides ................. .......... ................23
1.4 Solvent Extraction Processes for the Nuclear Waste Treatment. ................. ...............24
1.4.1 Extraction Processes with Extractants Containing Phosphorus Atoms ............26
1.4.1.1 PURE X process .............. ...............26....
1.4.1.2 TRUEX process ................. ...............26........... ....
1.4.1.3 TRPO process .............. ...............27....
1.4.1.4 DIDPA process .............. ...............27....
1.4. 1.5 UNEX process .............. ...... ...... ......... ........2
1.4.2 Extraction Processes with Incinerable Extractants .............. ....................2
1.4.2.1 DIAM EX process .............. ...............28....
1.4.2.2 SANEX process ................ ......... .......... .... ...............30....
1.4.3 Pre-organized Ligand Systems for Nuclear Waste Processing ................... ......31
1.4.3.1 Calixarenes .............. ...............32....
1.4.3.2 Cavitands .............. ...............32....
1.4.3.3 Tripodands .............. ...............33....
1.4.3.4 Trityls ................. ...............33........... ....
1.5 The Research Obj ectives ........._...... ...............35..._........

2 NEW NONADENTATE LIGANDS AS CANDIDATES FOR
ACTINIDE/LANTHANIDE SEPARATION: PYRIDINE-2, 6-DICARBOXAMIDE
DERIVATIVES OF THE TRIPHENOXYMETHANE PLATFORM BEARING
PYRIDINE-DIAMIDE MOEITIES .............. ...............43....


2.1 Ligand D esign ................... ..... ..._ ....... .. ...... .... .... ..... .......4
2.1.1 Recently Reported Extraction Studies with Pyridine-2, 6-dicarboxamides......45
2. 1.2 Research Objectives ................. ...............46......... ....



10











2.2 Synthesis of the Nonadentate Ligand Systems .....___.................. ... ..... ........... ....47
2.2.1 Synthesi s of Triphenoxymethane Platforms with Amine Groups...................47
2.2.2 Synthesi s of 6-(N, N-di alkyl carb amoyl)pyridine-2-carb oxyli c Aci d ...............4 8
2.2.3 Synthesis of the Ligands ................. ...............49........... ...
2.3 Conclusion .............. ...............50....
2.4 experimental Section............... ...............50
2.4.1 General Considerations .............. ...............50....
2.4.2 Synthesis .............. ...............51....

3 EXTRACTION EFFICIENCIES OF C3-SYMMETRIC NONADENTATE LIGAND
SYSTEMS WITH LANTHANIDE (III) CATIONS IN ACIDIC MEDIUM ........................65

3.1 Introduction ................. ...............65.................
3.2 Results and Discussion............... ...............6
3.2.1 Extraction Experiments ................... ... ........ .... ......... .. ... ......6
3.2.2.1 Extraction Pproperties of the ligands with the upper side
functionalized triphenoxymethane platform .............. .............. .67
3.2.2.2 Extraction properties of the ligands with the lower side
functionalized triphenoxymethane platform .............. .............. .68
3.2.2.3 Following the extraction efficiency of 2-13 by NMR
spectroscopy ............. .......... ........ ..... ...................7
3.2.3 Solid State Structures of 2-10, 2-13, and [2-10 M]3+, (M=Tm, Yb) ...............72
3.3 The Factors Affecting the Extraction Performance of Nonadentate Pyridine-2, 6-
dicarboxamide System .............. ...............76....
3.3 C conclusion .............. ... .. .. ..... .................... .... .................8
3.4 General Procedure for the Preparation of [2-10Ln] [Ln(NO3)5] [NO3] (Ln= Tm,
Yb) ................ .... ...............8
3.5 X-ray Crystallography............... ............8

4 INTRODUCTION ................. ...............85.......... ......


4.1 Porphyrins ........................ .......... ... .. .. .. .. .... ........8
4.2 Gouterman' s Four Orbital Model for the Spectroscopic Properties of Porphyrins ......85
4.3 Theory and Computational Chemistry ................ ...............88........... ...
4.3.1 General aspects of Quantum Chemistry ................. ............... ......... ...88
4.3.2 Basis Sets ................... ...............91..
4.3.3 Density Functional Theory............... ...............93.
4.3.3.1 Hohenberg-Kohn theorems............... ...............93
4.3.3.2 Kohn-Sham equations............... ...............9
4.3.4 Electronic Spectroscopy ............ .....____ ...............96...

5 COMPUTATIONAL CALCULATIONS FOR CIS-AZULENEONE AND 7RANS-
AZULENEONE ............ ..... ._ ...............101...


5.1 Computational Approach to Porphyrins and Porphyrin Derivatives ..........................101
5.2 Computational Methods ............ ...... .._ ...............102.













6 MOLECULAR ORBITAL APPROACH FOR THE ELECTRONIC EXCITED
STATES OF CIS-AND 7RANS-AZULENEONE .....__.....___ ..............._........10


6.1 Molecular Structures .............. ... .... ...._... ... .._. ...................10
6.2 Calculated Orbitals and the Spectra for the cis- and trans- Derivatives of
Azul eneone .............. ......... ...............106..
6.2.1 Kohn-Sham Orbitals .............. ...............108....
6.2.2 Excited States ............... ... .......... .......... ... ... ........1 2
6.2.2.1 Q-band regions for cis-Azuleneone and trans-Azuleneone ..............112
6.2.2.2 B-band regions for cis-Azuleneone and trans-Azuleneone............_116
6.2.2.3 Oscillator strengths ................. ...............118.......... ....
6.3 Conclusion ..............._ ...............119........_ ......


7 SUM M ARY ................. ...............126......... ......


APPENDIX: EXTRACTION DATA ........ ................. ...............128.....


LIST OF REFERENCES ........ ................. ...............157.....


BIOGRAPHICAL SKETCH ..............._ ...............166........_ ......











LIST OF TABLES


Table page

3-1 X-ray data for the crystal structures 2-10, 2-13, and the metal complexes of 2-10
with Tm and Yb. ............. ...............74.....

3-2 Selected bond lengths (A+) for the 2-10, 2-13, and metal complexes of 2-10 with Tm
and Y b. .............. ...............77....

6-1 Selected experimental and calculated angles on the porphyrin core for 5-la and 5-1b. .106

6-2 Calculated Molecular Orbitals, Symmetries and Energies (eV) for 5-1b and 5-2b.........109

6-3 Calculated electronic excited states, orbital configurationSa, b (% Weight), transition
energies and oscillator strengths for the first fifteen singlet states for 5-1b and 5-2b.....113

A-1 Extraction data for Figure A-1 ................. ...............128.____ ..

A-2 Extraction fata for Figure A-2............... ...............129..

A-3 Extraction data for Figure A-3 ................. ...............130....... ...

A-4 Extraction data for Figure A-4. .........._.._. .......... ...............131..

A-5 Extraction data for Figure A-5 ................. ...............132........ ...

A-6 Extraction data for Figure A-6. ..........._ ..... ..__ ...............133.

A-7 Extraction Data for Figure A-7. ............. ...............134....

A-8 Extraction data for Figure A-8 ................. ...............135..............

A-9 Extraction data for Figure A-9 ................. ...............136..............

A-10 Extraction data for Figure A-10 ................. ...............137........... ..

A-11 Extraction data for Figure A-11................. ...............138........... ..

A-12 Extraction data for Figure A-12. ................. ...............139....___ ...

A-13 Extraction data for Figure A-13 ................ ...............140........... ..

A-14 Extraction data for Figure A-14. .........._.._. .......... ...............141.

A-15 Extraction data for Figure A-15 ..........._ ..... ..__ ...............142

A-16 Extraction data for Figure A-16. ..........._ ..... ..__ ...............143.











A-21 Extraction data for Figure A-21 ................ ...............148.............

A-22 Extraction data for Figure A-22 ................. ...............149..............

A-24 Extraction data for Figure A-24 ................. ...............151..............

A-25 Extraction data for Figure A-25 ................ ...............152..............

A-26 Extraction data for Figure A-26 ................. ...............153..............

A-27 Extraction data for Figure A-27 ................. ...............154..............

A-28 Extraction data for Figure A-28 ................. ...............155..............

A-29 Extraction data for Figure A-29 ................. ...............156..............











LIST OF FIGURES


Figure page

1-1 Schematic representation of a tricapped trigonal prismatic geometry ............... .... ...........37

1-2 Schematic structure of chloro-COSAN ion.. ............ ...............37.....

1-3 Selected phosphorus containing extractants. ............. ...............38.....

1-4 Selected diamide extractants ................. ...............39................

1-5 Selected pyridine bearing heterocyclic extractants ................. .............................40

1-8 Trityl ligand systems............... ...............42

2-1 Structures of a. N, N, N', N'-tetraethylpyridine-2, 6-dicarboxamide and its tripodal
derivatives with b.TREN and c.Me-TRPN. .............. ...............60....

2-2 Structures of some recently studied DPA ligands............... ...............61

3-1 NMR scale extraction data with 2-13. ............. ...............82.....

3-2 Crystal structure of 2-10. ........._ .. ........_. ...............83...

3-3 Crystal structures of [2-10 M]3+, M= Tm, Yb. ............. ...............83.....

3-4 Crystal structure of 2-13. ................ ...............84.._..__ ...

4-1 Structure of porphyrin. ........._... ...... .___ ...............99....

4-2 Gouterman' s four orbital model for a D4h porphyrin. ......___ ..... ... ...............99

4-3 Possible transitions among the four orbitals of the porphyrins with the change of
ordering of the orbital s............... ...............10

4-4 The transitions for absorption and emission between the ground and excited states..... .100

5-1 Schematic representation of a. cis- Azuleneone, 5-la, and its simplified derivative
5.1b created for the calculations b. trans-Azuleneone,~trtrtr~r~r~ 5-2a Sand its simplified
derivative 5-2b used in the calculations............... .............10

6-1 Crystal structure of 5-la. ........._... ...... ___ ...............119.

6-2 Experimental bond lengths for 5-la. ........._._._. ....___ ...............120

6-3 Calculated bond lengths for 5-1b. .............. ...............120....

6-4 Calculated bond lengths for 5-2b ........._... ...... ..... ...............121..










6-5 Numbering scheme for the cis isomer for the selected atoms. ............. ....................121

6-6 Experimental and calculated electronic spectra for 5-1b ................ .......................122

6-7 Experimental and calculated electronic spectra for 5-2b ..........._... ......_.._............122

6-8 Kohn Sham orbital energy diagrams for some of the frontier orbitals of 5-1Ib and 5-
2b, respectively. ............. ...............123....

6-9 Isoamplitude surfaces of the wave functions of 5-1b and 5-2b for some of their
frontier orbitals, respectively. ............. ...............124....

6-10 Gaussian broadening curve and the actual Uv-Vis spectrum for the cis isomer. ............125

6-11 Gaussian broadening curve and the actual Uv-Vis spectrum for the transrt~t~rt~t~rt~t~rt~ isomer..........125

A-1 Extraction plot for 1x10-3 M 2-10 in CH2 12 with 1x10-4 M Lanthanides in 1 M
HNO3 ................. ...............128................

A-2 Extraction plot for the second extraction forlx10-3 M 2-10 in CH2 12 with 1x10-4 M
Lanthanides in 1 M HNO3. ............. ...............129....

A-3 Extraction plot for the third extraction for 1x10-3 M 2-10 in CH2 12 with 1x10-4 M
Lanthanides in 1 M HNO3. ............. ...............130....

A-4 Extraction plot for 7.63x10-3 M 2-10 in CH2 12 with 1x10-4 M Lanthanides in 1 M
HNO3 ................. ...............13. 1...............

A-5 Extraction plot for 1x10-3 M 2-10 in 1-Octanol with 1x10-4 M Lanthanides in 1 M
HNO3 ................. ...............132................

A-6 Extraction plot for 1x10-2 M 2-10 in 1, 2-dichloroethane with 1x10-3 M CO SAN with
lx10-4 M Lanthanides in 1 M HNO3 ................. ...............133........... .

A-7 Extraction plot for 1x10-3 M 2-11 in CH2 12 with 1x10-4 M Lanthanides in 1 M
HNO3 ................. ...............134................

A-8 Extraction plot for 1x10-3 M 2-12 in CH2 12 with 1x10-4 M Lanthanides in 1 M
HNO3 ................. ...............135................

A-9 Extraction plot for the second extraction for 1x10-3 M 2-12 in CH2 12 with 1x10-4 M
Lanthanides in 1 M HNO3. ............. ...............136....

A-10 Extraction plot for 1x10-3 M 2-13 in CH2 12 with 1x10-4 M Lanthanides in 1 M
HNO3 ................. ...............137................

A-11 Extraction plot for the second extraction for 1x10-3 M 2-13 in CH2 12 with 1x10-4 M
Lanthanides in 1 M HNO3. ............. ...............138....










A-12 Extraction plot for the third extraction for 1x10-3 M 2-13 in CH2 12 with 1x10-4 M
Lanthanides in 1 M HNO3. ............. ...............139....

A-13 Extraction plot for 1x10-4 M 2-13 in 1, 2-dichloroethane with 1x10-3 M CO SAN with
lx10-4 M Lanthanides in 1 M HNO3 ................. ...............140........... .

A-14 Extraction plot for the second extraction for 1x10-4 M 2-13 in 1, 2-dichloroethane
with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3 .............. .... ........._..141

A-15 Extraction plot for the third extraction for 1x10-4 M 2-13 in 1, 2-dichloroethane with
lx10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3. ................ ................ ..142

A-16 Extraction plot for 1x10-3 M 2-13 in 1, 2-dichloroethane with 1x10-3 M CO SAN with
lx10-4 M Lanthanides in 1 M HNO3 ................. ...............143........... .

A-17 Extraction plot for the second extraction for 1x10-3 M 2-13 in 1, 2-dichloroethane
with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3 .............. .... ........._..144

A-18 Extraction plot for 1x10-3 M 2-14 in 1, 2-dichloroethane with 3x10-3 M CO SAN with
lx10-4 M Lanthanides in 1 M HNO3 ................. ...............145........... .

A-19 Extraction plot for 1x10-3 M 2-15 in 1-Octanol with 1x10-4 M Lanthanides in 1 M
HNO3 ................. ...............146................

A-20 Extraction plot for the second extraction for 1x10-3 M 2-15 in 1-Octanol with 1x10-4
M Lanthanides in 1 M HNO3 ................. ...............147..............

A-21 Extraction plot for the third extraction for 1x10-3 M 2-15 in 1-Octanol with 1x10-4 M
Lanthanides in 1 M HNO3. ............. ...............148....

A-22 Extraction plot for 1x10-3 M 2-15 in 1-Octanol with 3x10-3 M COSAN with 1x10-4
M Lanthanides in 1 M HNO3 ................. ...............149..............

A-23 Extraction plot for 1x10-3 M 2-15 in CH2 12 with 3x10-3 M COSAN with 1x10-4 M
Lanthanides in 1 M HNO3. ............. ...............150....

A-24 Extraction plot for the second extraction for 1x10-3 M 2-15 in CH2 12 with 3x10-3 M
COSAN with 1x10-4 M Lanthanides in 1 M HNO3. ................ .......... ................1 51

A-25 Extraction plot for the third extraction for 1x10-3 M 2-15 in CH2 12 with 3x10-3 M
COSAN with 1x10-4 M Lanthanides in 1 M HNO3. ................ .......... ................1 51

A-26 Extraction plot for 1x10-4 M 2-15 in 1, 2-dichloroethane with 1x10-3 M CO SAN with
lx10-4 M Lanthanides in 1 M HNO3 ................. ...............153........... .

A-27 Extraction plot for 1x10-3 M 2-16 in CH2 12 with 1x10-4 M Lanthanides in 1 M
HNO3 ................. ...............154................









A-28 Extraction plot for 1x10-4 M 2-16 in 1, 2-dichloroethane with 1x10-3 M COSAN
with 1x10- M Lanthanides in 1 M HNO3. ............. ...............155....

A-29 Extraction plot for the second extraction for 1x10-4 M 2-16 in 1, 2-dichloroethane
with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3 .............. .... ........._..156










LIST OF SCHEMES

Scheme pg

2-1 Reaction scheme for the synthesis of 2-6, 2-7, 2-8 and 2-9 ................. ........__. ........62

2-2 Synthetic scheme for 2-5. ........._._. ........... ...............62....

2-3 Synthesis of 2-10 and 2-11. ........._.._.._ ...............63........._.

2-4 Synthetic scheme for 2-12. ............. ...............63.....

2-5 Synthesis of 2-13 and 2-15 ........._.._.. .......... ...............64.

2-6 Synthesis of 2-14 and 2-16. ................ ...............64......... .













































19









Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy

C3-SYMMETRIC NONADENTATE LIGAND SYSTEMS BEARING BOTH PYRIDINE AND
DIAMIDE MOIETIES FOR THE EXTRACTION OF LANTHANIDES AND ACTINIDES
AND DFT LEVEL COMPUTATIONAL STUDIES FOR THE MOLECULAR ORBITALS
AND ELECTRONIC TRANSITIONS OF EXPANDED PORPHYRIN SYSTEMS BEARING
BIS(NAPHTOAZULE~NEONE RING SYSTEMS

By

Ozge Ozbek

December 2007

Chair: Michael J. Scott
Major: Chemistry

Separation of radioactive actinides from lanthanides in nuclear waste is important since

transmutation of actinides in the presence of lanthanides is impossible. Nonadente ligands were

synthesized with the introduction of unsymmetrical pyridine-2, 6-dicarboxamide groups to the

preorganizing triphenoxymethane platform. The new incenerable ligand systems have the

advantage of combining both the pyridine and diamide groups on one platform to work

cooperatively for the extraction of trivalent metals from acid solutions. Ligand systems with two

different types of triphenoxymethane platforms, lower side functionalized triphenoxymethane

platform and upper side functionalized triphenoxymethane platform, have been synthesized. The

results of the extraction experiments with trivalent lanthanides in 1 M nitric acid solutions reveal

that all the ligand systems show moderate extraction of lanthanides by themselves but when the

synergist CO SAN is used, enhanced extraction behaviors are observed with lower side

functionalized ligands except with the ligand with octyl protected platform with isopropyl groups

as substituents. The results indicate that the solubility of the complexes forming during the

extractions and the relative concentrations of the synergist COSAN, the extraction ligand and the









metal play maj or role for the extraction behaviours of the ligands. Also, solid state structures of

the complexes with upper side functionalized ligand with Tm and Yb indicate the geometry

around metal is tricapped trigonal prism as expected for the metal complex with lanthanide (III)

ions. The synthesis of the ligands and the results of the extraction experiments are discussed

herein. The efficiencies of the ligands are compared.

The electronic properties of the expanded porphyrin systems, cis- and trans-azuleneone

derivatives, were of interest and computational studies of these molecules have been performed

at DFT level. Excited state calculations were performed with TDDFT. The calculated and

experimental geometries for the cis- isomer were compared and the results were determined to be

in good agreement. Calculated excited states for each of the molecules were also consistent with

the experimental spectra of the molecules. Detailed analysis of the calculated orbitals, orbital

energies and both the experimental and the calculated spectra of the molecules revealed that the

cis- isomer has split Q band region due to electronic affects of the substituents and symmetry

lowering. Also the B-band regions of both of the molecules show contributions coming from

lower lying orbitals. Both the experimental and theoretical results reveal that both of the

molecules are red shifted due to 2n- conjugation. All the details of the analysis and comparisons

of the calculated and experimental data are discussed herein.









CHAPTER 1
INTTRODUCTION

1.1 Nuclear Waste

Radioactive materials are used for different purposes and among them production of

energy is the most important one. By using nuclear energy, electricity is produced at nuclear

power plants.' Today, the electricity generated with nuclear power provides 15 % of the total

electricity generated around the world.2 The demand for energy is increasing more and more

every day with the development of technology. Search for economic and environmentally

friendly source of energy to replace fuel energy is underway. In this aspect, nuclear energy is a

good candidate for future energy production.

Nuclear energy production has one maj or problem to be solved. The use of radioactive

materials causes the generation of nuclear waste. As a result, the contamination of the

environment by radioactive materials and their negative impacts on the health of individuals is a

growing public concern.3 Actinides (An), present in nuclear waste, are some of the most

dangerous radioactive elements because they have long half-lives and activity. The half lives of

the actinides range between a few hundred years and a few thousand years or more.4 Even small

amounts of these nuclides can cause severe health hazards.3 During the decay of unstable nuclei,

a, p, or y rays are emitted with very high energy which can cause biological damage resulting in

cancer' or genetic disorders.5, 6

Due to the potential dangers of actinides in nuclear waste, waste reprocessing is essential

to provide both human and environmental safety. For the reprocessing of the waste, research has

been done for the separation of lanthanide (III) ions from chemically similar actinide (III) ions.

There are three maj or ways to manage nuclear waste: recycling of the actinides, direct

geological disposal of the waste and long term monitoring of the waste.' Currently, actinide









recycling and short term monitoring are the most common approaches used. The lifetime of

natural and engineered barriers proposed for long term storage is under question. Therefore it

possesses a safety threat.'

1.2 Nuclear Incineration of Trans-Uranium Actinides: Transmutation

The primary goal of nuclear waste reprocessing is transmutation which is the conversion of

long-lived minor actinides (e.g. americium), into short-lived isotopes by neutron bombardment.8

9 During this process, energy and neutrons are released in addition to fission products. The

fission products remain radioactive but they decay in a shorter time than the parent molecule.

The transmutation process is very important for long term nuclear waste management. The

success of the transmutation process requires pure targets.'0 Therefore separation of trivalent

actinides from trivalent lanthanides is necessary; otherwise the lanthanides absorb neutrons and

prevent neutron capture by the transmutable actinides.ll

1.3 Chemical Properties of Lanthanides and Actinides

Although transmutation provides an efficient way of converting long-lived minor actinides

into short-lived isotopes, it is generally not applicable because trivalent actinides and trivalent

lanthanides coexist in most nuclear waste. Efficient separation of actinides and lanthanides is a

challenge because actinide (III) cations heavier than plutonium (Pu) are chemically similar to

lanthanide (III) cations.

The trivalent charge is commonly observed for most lanthanide and actinide ions except

for the early (thorium and plutonium) actinides or the late actinide nobelium because the actinide

5f orbitals have smaller spatial distribution and energy than the series and special distributions of

6d, 7s, and 7p orbitals.12 The spatial distribution of actinide 5f orbitals are greater compared to

the 7s and 7p orbitals than the spatial distribution of the lanthanide 4f orbitals with respect to the

6s and 6p orbitals. The larger spatial distribution of actinide 5f orbitals makes them slightly more









covalent than the lanthanides.13 In a study, it was reported for Am and Eu that, the sigma bond

energy of Am is higher than that of Eu with sulfur which indicates that spatial extent of 5f

orbitals play a crucial role for the covalency in spite of their higher orbital energy.14 Moreover

the interaction of the metallic core with the surrounding ligands in coordination complexes of

lanthanide (III) ions is mainly electrostatic because the 4f valence shells of the trivalent

lanthanides are shielded from external perturbations by the filled 5s2 and 5p6 Orbitals."5

The greater covalency of the trivalent actinides with respect to trivalent lanthanides is the

only significant difference between these two f block elements. Therefore ligands with softer

donor atoms, such as N, S or C1 relative to oxygen are suggested for the discrimination of

actinides from lanthanides.12

Variable coordination numbers and geometries have been observed both for tripositive

lanthanide and actinide ions. The observed coordination numbers for the lanthanide (III) ions

range between 6 and 12.16, 17 Nine coordination is common for the lanthanide (III) ions and

several complexes are reported having tricapped trigonal prismatic geometry with nine

coordination sites.18, 19, 20 Nona aqua complexes of lanthanide (III) ions are in tricapped trigonal

prism geometry. The tricapped trigonal prismatic geometry is depicted in Figure 1-1.

1.4 Solvent Extraction Processes for the Nuclear Waste Treatment

Safe disposal of nuclear waste is a primary concern, and to this end, the development of

separation techniques for trivalent actinides from trivalent lanthanides is essential for the nuclear

waste reprocessing. Research studies have been focused on liquid-liquid extraction processes

because it is the most successful technique. During liquid-liquid extraction, the charged metal

ion is extracted as a complex with an extract ant from a highly acidic aqueous phase into an

immiscible organic phase.21 For effective separation the legends of the extract ant should have

minimal solubility in the aqueous phase.22 The complication reaction occurs in the interfacial









zone between the organic and aqueous phases.22 The extent of extractability of the metal is

measured by the distribution ratio (D), which is the ratio of concentration of the metal in the

organic phase to its concentration in the aqueous phase. Also of importance is the separation

factor (SF) which is the ratio of the distribution ratios of lanthanide and actinide ions, indicating

the selectivity of the extractant.8

Lanthanide and actinide captions are transferred from the aqueous solution into the organic

phase in tight complex formation. During this process, the metal is surrounded by the uncharged

ligands to form a charged complex. In addition to the complex, hydrated nitrate anions can be

transferred to the organic phase with the metal cation.23

When cobalt bis(dicarbollide) anion (1-), closo-[(1,2-C2B9H1 )2-3,3'-Co]~, COSAN, is used

as a coextractant enhanced extraction ratios are sometimes observed.24 The ion pair formation

with the charged complex and the CO SAN is due to the great hydrophobicity of the CO SAN

anion.24 This way hydration of the complex is lowered so that it becomes more soluble in the

organic phase. The chemical stability of CO SAN in nitric acid is enhanced by the halogenation

of the most reactive terminal hydrogen atoms. COSAN derivatives are stable to radiation. In

Figure 1-2 the structure of chloro-COSAN is depicted. Since CO SAN derivatives are insoluble in

hydrocarbons, moderately polar solvents, such as aromatic nitro compounds, halogenated ethers,

etc., are used for the extractions.25

The first step of nuclear waste reprocessing is the dissolution of used fuel rods in nitric

acid. Initially, several processes have been developed including the PUREX, TRUEX, TRPO,

DIDPA, and UNEX processes. In PUREX process industrial uranium and plutonium are

recovered from the generated waste. TRUEX process removes actinides and lanthanides from the

liquid waste that was generated during PUREX process. Although these processes are successful









in terms of selectivity and high extraction efficiencies of the extractions, they all involve

phosphorus containing reagents which creates a secondary waste stream.26 As an alternative to

TRUEX process and the other processes, incinerable processes containing only carbon, oxygen

hydrogen and nitrogen atoms are being developed to minimize generation of secondary waste,27

and utilizing diamides, the DIAMEX process is among the most promising ones.27 Another

approach to incinerable extraction systems is SANEX process. SANEX process employs

pyridine, pyrazolone and other heterocyclic molecules as ligands to make the coordination site

more covalent in nature and increase the selectivity for actinides.12, 26, 27

1.4.1 Extraction Processes with Extractants Containing Phosphorus Atoms

1.4.1.1 PUREX process

The PUREX (Plutonium and Uranium Reduction Extraction) process efficiently isolates U

and Pu from the mixture of fission products.28 With a water immiscible organic phase such as

tributylphosphate (TBP), the unwanted metal ions (fission products) are extracted into the nitric

acid medium and Pu (IV) and U (IV) move into the organic phase. 27 The structure of TBP is

given in Figure 1-3.

There are three purification cycles. Although 99.9% of the fission products are separated in

the first cycle, to increase the efficiency of the separation the same process is repeated in the

second and third cycles.27 During the first cycle U (IV) and Pu (IV) are extracted with TBP, and

then Pu (IV) is reduced to Pu (III). In this way Pu (III) and U (IV) are separated from each other

with another extraction since Pu (III) is less extracted than U (IV) with TBP. The last step

involves the uranium stripping from the TBP phase.27

1.4.1.2 TRUEX process

The transuranic element extraction (TRUEX) process is a liquid-liquid extraction process

for the recovery of actinides from liquid waste.29 For this process octyl(phenyl)-N, N-









diisobutylcarbamoylmethylphosphine oxide (CMPO) is used as an extractant with paraffin

diluents.30 The structure of CMPO is shown in Figure 1-3. TBP is also used as a solvent

modifier as it enhances the extraction of metal cations.29 Detailed research has been carried out

for the distribution behavior of the TRUEX process for the actinides, lanthanides and some

fission products29, 30 CMPO is a very powerful extractant. It is reported that greater than 99.99%

of Am from the organic phase could be removed by using simulated waste solutions with

CMPO.27 During the process, chelating CMPO binds the M3+ cation tightly by its C=0 and P=0

donor atoms. After the formation of the cation complex, polar nitrate ions are transferred

together with the cation for charge compensation.31

1.4.1.3 TRPO process

Actinides with (III), (IV) and (VI) oxidation states are extracted from nitric acid by

trialkylphosphine oxide extractants (Cyanex 923). U (VI), Np (IV, VI) and Pu (VI) are extracted

with 99% by using TRPO (with alkyl chains C6 to C8) in kerosene.27 The structure of TRPO can

be seen in Figure 1-3. TRPO/TBP mixture in kerosene reportedly showed high extractability for

UO22+ 32

The TRPO process is advantageous due to the low cost of the trialkylphosphine oxide

reagents and high extraction efficiency for several actinide and lanthanide elements.27 However,

the process has the disadvantage of being efficient at only dilute nitric acid concentrations, which

increases the amount of the liquid waste to be treated. 27

1.4.1.4 DIDPA process

In this process diisodecylphosphoric acid (DIDPA) is used as the extractant. In Figure 1-3

the structure of DIDPA is given. U(VI), Pu(IV), Np(IV), Am(III), Cm(III) and lanthanides (III)

are successfully extracted with a mixture of DIDPA and TBP at certain concentration. Numerous

studies with dialkylphosphoric acids, of the di-2- ethylhexylphosphoric acid (D2EHPA) type,









dialkyldithiophosphinic acid (Cyanex 301) or their synergistic mixtures with neutral

phosphorous extractants have been done for the extraction of Nd(III), U(VI), Th(IV), Am(III)

etc., from nitric acid solutions and efficient extractions for trivalent actinide/lanthanide elements

are achieved.27, 33, 34 The structure of Cyanex 301 is shown in Figure 1-3.

The disadvantages of DIDPA process are similar to those of TRPO. This process also

requires high dilutions and denitration resulting in a greater volume of waste solution to be

treated.27

1.4.1.5 UNEX process

The universal extraction (UNEX) process uses a synergistic mixture containing the

hexachloro derivative of cobalt dicarbollide (CCD), polyethylene glycol (PEG) and

diphenylcarbamoylmethylphosphine oxide.4 CS (I), Sr (II) and several actinides and lanthanides

are extracted. CCD extracts Cs (I), PEG extracts Sr (II) and the CMPO extracts the

actinide/lanthanide metals.27 When the waste solution was diluted with HF to prevent huge

extraction of Fe and Zr instead of Eu (III), promising results were obtained. Several research

studies are being done for the optimization of the UNEX process.27

1.4.2 Extraction Processes with Incinerable Extractants

1.4.2.1 DIAMEX process

The DIAMEX (Diamide Extraction) process was developed for the selective co-extraction

of trivalent actinides and trivalent fission lanthanides from nuclear waste.35 The diamide

extractants used for this process, such as malonamides, succinamide, glutalamide and adipamide,

are incinerable. These compounds are weak bases in which the carbonyl amide groups coordinate

to metal ions in a chelate complex.36 They have strong complexation with the metal ion and are

able to extract metal ion from highly acidic solutions.37 Either one or two malonamides are

bound to the lanthanide ion and nitrate ions and/or water molecules complete the coordination









sphere of the metal.38 In CryStal structures of Am3+ and Nd3+ with N, N, N', N'-

tetraethylmalonamide, TEMA, both of the metal ions have the same coordination geometry with

two TEMA molecules coordinating through their carbonyl groups and the remaining

coordination sphere is completed with three bidentate nitrate ions.39 The structure of TEMA is

depicted in Figure 1-4.

Among the malonamides used for the extraction purposes, N, N-dimethyl- N, N-

dibutyltetradecylmalonic diamide (DMDBTDMA) was proposed as a promising extractant.35

Recent studies suggest that N, N-dihexyl octanamide (DHOA), N, N-di(2-ethylhexyl)

isobutyramide (D2EHIBA), and N, N'-dimethyl-N, N' -dioctyl-hexylethoxy-malonamide

(DMDOHEMA) are good extractants as well.40, 41 The structures of DMDBTDMA and

D2EHIBA can be seen in Figure 1-4. N-dihexyl octanamide (DHOA) and N, N-di(2-ethylhexyl)

isobutyramide (D2EHIBA) are proposed to be a promising alternative for TBP for uranium-

based fuels.40 Analysis with N, N-dimethyl-N, N-dioctyl-hexylethoxy-malonamide

(DMDOHEMA), seen in Figure 1-4, has shown that because of increased lipophilicity, it is

highly resistant to hydrolysis and radiolysis.41 In another recent study, the efficiency of N, N, N,

N- tetraoctyl-3 -oxapentane-1, 5-diamide (TODGA) was investigated, and it showed high

extractability with trivalent metal ions.42 For the extraction of Eu(III), Am(III), Th(IV), and

U(VI), N, N'-dimethyl-N, N'-dihexyl-3 -thiopantanediamide (DMDHTPDA) was used as an

extractant.43 When used alone, none of the cations were extracted into the organic phase because

of very weak complexation due to the presence of sulfur atom, a very soft base. Although

extraction experiments were performed using synergistic thenoyltrifluoroacetone except with the

ion of the Th (IV) system, the separation factors were smaller for this ligand than those of

thenoyltrifluoroacetone and N, N'-dimethyl-N, N'-dihexyl-3 -oxapentanedi amide (DMDHOPDA)









which is the oxo ether analog of DMDHTPDA.43 TODGA and DMDHOPDA are also depicted

in Figure 1-4.

Earlier, ether type diamides with oxygen or nitrogen introduced into carbon chain between

the two amide groups were synthesized and analyzed for their extraction behaviors.37 It was

determined that the extractability of diglycolamide (DGA) for actinides is greater than that of

malonamide.44 The ether oxygen in DGA is important for chelation to actinides, showing

tridentate coordination. Another important factor is the length of the alkyl chain attached to the

N atom of the amide group, which determines the distribution ratios and solubility of the amide

in diluent.44 In another study with ether type ligands, extraction experiments were performed

with N, N'-dimethyl-N, N'-dihexyl-3 -oxapentanediamide, (DMDHOPDA), N, N'-dihexyl-3-

thiopentanediamide, (DHTPDA), and N,N'-dihexyl-3-oxapentanediamide, (DHOPDA).

Extraction data revealed that no pH dependence was observed with DMDHOPDA for Eu3+,

Am3+, Th4+, NpO2+ and UO22+ ionS.37

1.4.2.2 SANEX process

Nitrogen heterocycles are promising for the separation of actinides(III) from nuclear

waste.45, 46 The ligands 2, 2':6' 2"-terpyridine and 2, 4, 6-tri(2-pyridyl)-1, 3, 5-triazine have been

used, and separation factors between Am(III)/Eu(III) 7 and 12 were obtained, respectively. These

ligands required a weak organic acid as synergist.8, 46

The most efficient ligands are the ones bearing either 1, 2, 4-triazine or 1, 2, 4-triazole

groups incorporated into a tridentate ligand.47 Alkylated 2, 6-di(1, 2, 4-triazin-3 -yl)pyridines

(BTP) have been reported to be very powerful extractants.8, 9, 22, 45- 50 These ligands are able to

attain separation factors for americium or curium versus europium of more than 100 in up to 1 M

nitric acid solution.8, 45, 47, 49 The structure for BTP is given in Figure 1-5.









The reason for the high selectivity of these ligands is may be the soft donor nitrogen atoms

form stronger bonds with the more covalent actinides.22, 46, 48 The electron density on the

nitrogen atoms and the basic character of these ligands are the main factors for the coordination

of the metal ions with these ligands.47 During extractions, the ligand coordinates to the metal

through the nitrogen of its central pyridine and the nitrogen atoms at the 2-position of the

triazinyl rings.22 The ligand forms [ML3 3+ type cations which enable the phase transfer

possible.47 A recent study brings up a different explanation for the selectivity of these ligands.

The greater thermodynamic stability of the actinide complexes in relation to that of the

lanthanide complexes may be responsible.45

Also 2, 2:6, 2-terpyridine, 2, 4, 6-tri s(4-alkyl-2-pyridyl)-1i, 3, 5-triazine, and 4-amino-bis(2,

6-(2-pyridyl))-1, 3, 5-triazine, were tested as extractants, and a variety of separation factors for

actinides over lanthanides were achieved.9 The ligand structures are shown in Figure 1-5.

Since 2, 6-di(5, 6-dialkyl-1, 2, 4-triazin-3 -yl)pyridines are susceptible to hydrolysis and

radiolysis, different ligand systems with 2, 6-dioxadiazolylpyridines, as seen in Figure 1-5, were

synthesized as mimics with the hope of overcoming the hydrolysis and radiolysis problems.47

Although varying separation factors were achieved, these extractants were not as efficient as 2,

6-bis(5, 6-dialkyl-1, 2, 4-triazin-3 -yl)pyridines.47

Also, extractant systems with 2, 6-bis (benzimidazol-2-yl) pyridine were synthesized but

the separation factors were not higher than 23.5

1.4.3 Pre-organized Ligand Systems for Nuclear Waste Processing

Preorganization of a ligand makes complexation to the target metal ion more facile since it

is already placed at a certain position that can collaborately work with the other lighting sites

already positioned.52 The system predisposed to the high number of coordination sites required

by the metal cation. The preorganized ligand systems are better extractants due to entropic









factors.2 The limited flexibility of the coordinating sites favors the coordination to the metal

compared to the competing solvent molecules or anions.2

1.4.3.1 Calixarenes

Calixarene platforms contain various functional groups positioned in a well defined

arrangement.53 The calixarene platform can be functionalized either at the lower rim surrounding

a smaller cavity or at the upper rim surrounding a larger cavity.2 The size of the platform

depends on the number of phenol groups; calix[3]arene being the smallest with three phenol

groups, and calix[8]arene being one of the biggest with eight phenol groups.2 Increasing the size

of the platform makes it more flexible and be able to have more conformations.2 Several

calixarene systems have been studied for extraction with mono54' 55 and bifunctional phosphine

oxideS2, 21, 56' 57 in addition to CMPO, the most investigated moiety with calixarenes, as seen in

Figure 1-6. All the systems studied thus far have indicated that with the reorganization

introduced by the calixarene systems, better extractions and selectivity are attained compared to

the same ligand systems without preorganizations.

In addition to phosphorus containing ligands, picolinamide systems have been studied.

However, due to protonation at high acidities in these systems, they did not prove to be as

interesting for industrial applications.2

1.4.3.2 Cavitands

Cavitands are structurally similar to calixarenes except that upper rim phenyl-phenyl

eythylene glycol bridges prevent phenyl rings rotation making them more rigid.2 Studies with

both CMPO and Cyanex 301 based ligands have been performed with cavitands.2' 52, 58 The

structure of a CMPO derivative of a cavitand is depicted in Figure 1-7 Although the extraction of

Am(III) was enhanced with a cavitand system bearing CMPO, it was not as effective as the

calixarene derivative.2 The selectivity of Eu(III) over UO2(II) and Fe(III) was higher with CMPO









cavitand systems than simple CMPO systems.52 COHVersely, tetrakis(phosphane sulfide)

cavitands are ineffective for the extraction of Am(III).5

1.4.3.3 Tripodands

Tripodands are very flexible C3-Symmetric platforms with a central carbon atom to which

three identical arms are attached with metal binding sites. An R group is also attached to the

central carbon atom to control the solubility.2 In a recent study reasonable extractions were

obtained with Eu (III) and Am (III) with CMPO groups in the presence of a synergistic Br-

COSAN with tripodand systems.59 The CMPO tripodand is depicted in Figure 1-7.

1.4.3.4 Trityls

Trityl platforms are C3-Symmetric platforms with three phenol groups attached to a single

carbon atom from their meta positions. In the triphenoxymethane platforms, the oxygens of the

phenol groups were determined to be pointing up, parallel to the central hydrogen atom.60

Ligands based on the triphenoxymethane platform are advantageous because they can be

prepared quickly in bulk quantities, the solution and solid state structures of the complexes can

be fully characterized, and the solubility properties can be easily changed by making adjustments

to the substituents on the base of the platform. This platform can be functionalized either at the

oxygen atom of the phenol group (upper side functionalized triphenoxymethane platform) or at

the para- position (lower side functionalized triphenoxymethane platform).

A tris CMPO ligand system was developed with the upper side functionalized

triphenoxymethane platform.61 The crystal structures of Th(IV) and Nd(III) clearly indicated the

coordination of the preorganized CMPO ligands through C=0 and P=0 groups.61 In Simulated

waste extractions, the ligand system showed a high affinity for Th(IV) but very low affinity for

the lanthanide (III) series.61 The structure of this ligand is shown in Figure 1-8.









Inspired by the upper side functionalized CMPO triphenoxymethane system, Boihmer, et

al. introduced a C3-Symmetric lower side functionalized CMPO system with triphenoxymethane

platform,62 Shown in Figure 1-8. This ligand system revealed reasonable selectivity between

Am(III) and Eu(III) but it was not as effective as the calixarene systems for extractions from

highly acidic media.62

In addition to the CMPO system, another upper side functionalized ligand system was

synthesized with DGA as depicted in Figure 1-8.63 In this molecule three diglycolamides are

collectively providing nine coordination sites with their diamide moieties and their etheric

oxygen atoms to help to form C3-Symmetric metal complexes. This ligand revealed slightly

higher selectivity than its simple form between Eu (III) and Am (III). It also had higher affinity

for the heavier lanthanide (III) cations than the lighter ones in dichloromethane.63 When the

experiments were repeated with 1-octanol, the extractant showed selectivity for the lanthanide

ions in the middle of the series. When n-butyl substrates instead of isopropyl substrates were

used, the efficiency of the extraction dropped significantly. The selectivitiy of the ligand was

also lost.

Extraction experiments with 1-octanol and n-dodecane solvents with the n-butyl derivative

were unsuccessful due to phase separation problems.

According to the solid state structures obtained with DGA ligand with upperside

functionalized triphnoxymethane platform with isopropyl substrates with Yb, the geometry of the

complex is C3 Symmetric tricapped trigonal prism with coordination sites of diamide moieties

and the oxygen atoms in between. Oxygen atoms are coordinated to the metal and make the

tricapped part of the structure. The ligand fully saturated the coordination sphere of the metal

leaving no space for the nitrate ions to coordinate.









In order to achieve selectivity between the actinide and lanthanide ions, the etheric oxygen

in the middle was replaced by sulfur to make the thio derivative of the legend. However the

extraction experiments revealed that there were negligibly low distribution coefficients for this

ligand. The big sulfur atom was making the geometry of the complex to be distorted from the

tricapped trigonal prism geometry and resulting with poor metal binding. This also showed the

importance of the etheric oxygen in DGA derivative in terms of its binding and its effect for the

extraction experiments.

The DGA ligand was synthesized with the lower side functionalized triphenoxymethane

platform but the ligand showed no extraction with this type of triphenoxymethane platform.

1.5 The Research Objectives

The main goal of this proj ect was to design and synthesize new multidentate ligands by

exploiting triphenoxymethane platform, in order to test their extraction behaviors with trivalent

lanthanide cations in 1 M nitric acid solutions. The new ligands were to be tested in acid

solutions with lanthanide cations to determine the feasibility of their use for actual extraction

process of nuclear waste. The research also focuses on the characterization of the lanthanide (III)

complexes both in solution and solid state. Previously in our group, incenerable nonadentate

ligand systems bearing DGA groups with triphenoxymethane platform were synthesized and the

extraction behaviors of these ligands were studied in detail and it was observed that they showed

successful extraction performances. Having observed successful extractions with nonadentate

DGA ligands with triphenoxymethane platform and the reported success of heterocyclic ligands

bearing relatively softer nitrogen atoms led us to design a new incenerable ligand system bearing

both pyridine and diamide moieties. To create this ligand system three pyridine-2, 6-

dicarboxamide derivatives were introduced to triphenoxymethane platform to form a nonadentate

ligand system. Both upper side and lower side functionalized triphenoxymethane ligands were










prepared. Extraction experiments were performed in 1 M nitric acid solution with Ln(III) cations

to determine the extractabilities of these metals. Extraction experiments were repeated with

chloro-COSAN to enhance the extraction of the lanthanides with the new ligand systems.



























Figure 1-1 Schematic representation of a tricapped trigonal prismatic geometry


Cl

CH

BH


hexachloro bis(1,2-dicarbollide)cobaltate
Cl6COSAN ion

Figure 1-2 Schematic structure of chloro-COSAN ion.










O

H3C(H2 )30/ 'O(CH2 3CH3
O(CH2)3CH3


O O
I CH2CH(CH3)2
H3C(H2 7 CH2 N
CH 2C H(CH3)2


R-'R
R


(H3 2HHC(H2 70 'OH
O(CH2)7CH(CH3)2


R I'SH
R


Figure 1-3 Selected phosphorus containing extractants. A) TBP, B) CMPO, C) TRPO, D)
DIDPA, E) Cyanex 301.













O N


OO
N'\


H3C(H2 )5 O (CI
ON

/,N O


H2)7CH3

'(CHO7CH3


(CH2 5CH3 (CH2 5CH3

/ ON


C8H17 C8H17

Ce N CeH?817


Figure 1-4 Selected diamide extractants. A) TEMA, B) D2EHIBA, C) DMDOHEMA, D)
TODGA, E) DMDHOPDA.



































NH2





E R F R


Figure 1-5 Selected pyridine bearing heterocyclic extractants. A) BTP, B) 2,4,6-tris(4-alkyl-2-
pyridyl)-1 ,3,5-triazine, C) 2,2: 6,2-terpyridine, D) 2,6-bis(benzimidazol-2-yl)pyridine,
E) 4-amino-bis(2,6-(2-pyridyl))-1 ,3,5-triazine, F) 2,6-dioxadiazlylpyridine.






































n=1,2,3






Figure 1-6 Upper and lower rim functionalized calix[4]arenes with CMPO. A) Upper rim
functionalized ligand, B) Lower rim functionalized ligand.









P~h
Ph P=0
O

NR"

O,


Ph

N -Ph
R O


Ph' 1
Ph


O o


n=1,3


Figure 1-7 Cavitand and tripodand systems with CMPO. A) cavitand, B) tripodand system







PhO
Ph-P=0 R
Or O~ R


ii O O Y 3OPNH



P h Ph 3


A B C

Figure 1-8 Trityl ligand systems. A) Upper side functionalized triphenoxymethane platform with
CMPO groups, B) Upper side functionalized triphenoxymethane platform with
diglycolamide (DGA) groups, C) Lower side functionalized triphenoxymethane
platform with CMPO groups.









CHAPTER 2
NEW NONADENTATE LIGAND S A S CAND IDATE S F OR AC TINIDE/LANTHANIDE
SEPARATION: PYRIDINE-2, 6-DICARBOXAMIDE DERIVATIVES OF THE
TRIPHENOXYMETHANE PLATFORM BEARING PYRIDINE-DIAMIDE MOEITIES

2.1 Ligand Design

In the design of a ligand system for the separation of trivalent actinides from trivalent

lanthanides commonly found in nuclear waste, some important factors should be considered. The

first is that the ligand must be able to easily bind the metal cation and fulfill the required

coordination number of the metal coordination sphere. Since extraction experiments are typically

performed under highly acidic and radioactive conditions, the ligand should have high radiation

and chemical stability.64, 65 Also, the solubility of the ligand should be characterized.64 The main

purpose of the proj ect is to design a ligand for industrial applications so it is important to

consider the ease of its synthesis and purification and the material cost of the ligand.66 The

toxicity of the ligand and its degradation products are also important factors to be taken into

account.66

The main goal of nuclear waste treatment is the selective separation of the relatively more

covalent trivalent actinides from trivalent lanthanides. Therefore a ligand system bearing softer

donor atoms at its binding site relative to oxygen, such as N, or S, will be promising to enhance

covalent character at the binding site. Also, in order to not create additional waste, the ligand

system should be incinerable. Moreover, a ligand system exploiting reorganization will be more

advantageous for the purpose of extractions. Lastly, creating a ligand bearing a coordination site

mimicking that of those ligands previously reported to perform well in terms of extractability and

selectivity could be advantageous.

Keeping these important requirements in mind, we designed a nonadentate ligand system

having three asymmetric N, N-dialkylpyridine-2, 6-dicarboxamide moieties attached to a










triphenoxymethane platform. The novelty of the ligand stems from the fact that it combines both

pyridine and diamide binding sites. As mentioned before for the DIAMEX and SANEX

processes, diamides and nitrogen-bearing heterocyclic systems have high extraction and

selectivity towards trivalent f-block elements. Our proposed ligand system takes advantage of

both pyridine and diamide properties. This incinerable ligand system is also preferable due to its

reorganization which enables it to provide nine binding sites for the metal, with six carbonyl

groups (C=0) from diamide moieties and three nitrogen atoms from its pyridine moieties. This is

advantageous because trivalent f-block cations prefer high coordination numbers. Another

important characteristic of this ligand is that it has soft nitrogen atoms at its binding site to

enhance covalent character which confers the selectivity between the trivalent actinides and

lanthanides.

The selection of tridentate pyridine-2, 6-dicarboxamide (DPA)for extraction purposes

stems from the fact that the coordination chemistry of this ligand with trivalent lanthanides has

been extensively studied for its photophysical properties.15, 67-71 Not only does this ligand meet

all the requirements for the extractions, it provides an ideal coordination site for lanthanide (III)

cations. Tridentate ligands of the type N, N, N', N' -tetraalkylpyridine-2, 6-dicarboxamide

bearing both pyridine and diamide groups, produce stable lanthanide complexes of the type

ML33+ 67 Solution and solid state structural investigations for N, N, N', N' -tetraethylpyridine-2,

6-dicarboxamide indicated that in these complexes OC-N amidee) bonds exhibit considerable

double bond character, and that the alkyl residues are situated close to the three fold axis and the

metal ion. The structure of N, N, N', N' -tetraethylpyridine-2, 6-dicarboxamide is depicted in

Figure 2-1.









Tripodal ligands were also synthesized with DPA moieties. Three asymmetric tridentate

DPA moieties are connected to the tris(2-(N-methyl)aminoethyl)amine (TREN) tripod to give a

nine-coordinate podand that shows pseudo-tricapped trigonal prismatic geometry with Ln(III)

due to the orientation of the three tridentate ligands.69, 71 A similar type of tripodal ligand was

synthesized with tris(3-(N-methylamino)propyl)amine (Me-TRPN).70 In all of these studies the

stabilities of these complexes in solution were studied in addition to the formation of their

protonated adducts in acidic media. The structures of TREN and Me-TRPN bearing diethyl

derivative of DPA are given in Figure 2-1.

2.1.1 Recently Reported Extraction Studies with Pyridine-2, 6-dicarboxamides

Research has been sparingly performed with the pyridine-2, 6-dicarboxamides, DPAs, for

nuclear waste separation processes. Therefore limited information is available for these

molecules, most of which is quite recent and can be considered to be preliminary. These studies

reveal that DPAs do not extract metals from acidic solutions by themselves. However, in

combination with chlorinated derivative of COSAN, high extractions of Cs and actinides are

achieved.72

DPAs are weaker donors than malonamides. They also are less basic in character than

picolinamides because the second carboxamide group introduced into the molecule further

decreases the basicity of the pyridine nitrogen.73

Smirnov et al. worked on derivatives of DPA including tetraethyl DPA, tetra-n-butyl DPA,

N, N'-diphenyl-N, N'dimethyl DPA, N, N'-diheptyl DPA and tetra-i-butyl DPA.73 The structures

of these ligands are depicted in Figure 2-2. All of these extractants showed moderate extraction

of Am in nitric acid solution with metanitrobenzotrifluoride as diluent. However, when chloro-

COSAN is used, the distribution ratio (D ) for Am is quite high (>~10), which is comparable to

CMPO extractions. Another important factor is the selectivity for Am over Eu. Depending on









their results the separation factor is D~m/DEu > 2.6 for tetra-n-butyl DPA which indicates that the

system has potential for Am/Eu separation. The pyridine nitrogen is the likely reason for this

selectivity.73 Based on this data, DPAs have been proposed as a potential alternative to CMPO

for the extraction of actinides.73

In another study, N, N'-diethyl-N, N'-di (p-tolyl) DPA showed good extraction properties

in nitric acid with metanitrobenzotrifluoride as diluent.74 This ligand extracts Am better than Eu.

However, separation factors decrease with increasing solution acidity. Even 0.2 M ofN, N'-

diethyl-N, N'-di (p-tolyl) DPA is sufficient enough to recover Am, and is considered to be a

promising candidate for the separation process.74 The structure of this ligand is also given in

Figure 2-2.

In order to probe the effect of acid conditions, extractions with DPA were carried out in

perchloric acid with fluorinated solvents as the diluents.75 The extraction efficiency is much

higher in perchloric acid than in nitric acid. The extraction ability is dependent up on the

substituents on the nitrogen atoms, such that dialkyldiaryldiamides turned out to be better

extractant than di- and tetraalkyldiamides for Am and Eu. In spite of high extraction

performances in perchloric acid, the selectivity is lost.7

2.1.2 Research Objectives

In this study, two derivatives of DPA were introduced to derivatives of both upper and

lower side functionalized triphenoxymethane platforms to form unsymmetrical nonadentate

ligands for extraction purposes. These ligands were fully characterized and both their solid state

and solution structures were analyzed. Extraction experiments were performed in three different

solvents (1-octanol, 1, 2-dichloroethane and dichloromethane), with lanthanide (III) cations in 1

M nitric acid solution.









In this chapter the synthesis of these ligands will be described in detail. In the following

chapter the extraction experiments will be explained and the results of these experiments will be

discussed in detail and compared to recently reported studies involving DPAs.

2.2 Synthesis of the Nonadentate Ligand Systems

The key step of the synthesis of the ligands was the coupling reaction between the amine

groups of the triphenoxymethane platform and the carboxylic acid of the 6-(N, N,-

dialkylcarbamoyl)pyridine-2-carboxylic acid. For this purpose upper and lower side

functionalized triphenoxymethane platforms with amine groups were synthesized in addition to

the 6-(N, N, di alkyl -di arb amoyl)pyri dine-2-carb oxyli c acid derivatives.

2.2.1 Synthesis of Triphenoxymethane Platforms with Amine Groups

The upper side functionalized triphenoxymethane platforms, with three carbon linker

groups, (2-1),76 and two carbon linker groups, (2-2),7 were synthesized as reported. A synthetic

route was developed to make the lower side functionalized triphenoxymethane platform with the

amine group. First, 2, 2', 2"'-methanetriyltri s(4-nitrophenol) (2-3) was prepared according to the

literature method.'" In order to synthesize the lower side functionalized triphenoxymethane

platform, the phenol group of 2- 3 must be protected with an alkyl group. To this end alkylation

reactions were performed with a weak base and an alkyl iodide, RI, (R= methyl, octyl) The

synthetic scheme for these molecules, methyl protected 2-methoxy-5-nitrophenylmethane (2-6)

and octyl protected tris(5-nitro-2-(octyloxy)phenylmethane (2-7) are depicted in Scheme 2-1.

The first method that was used to synthesize 2-6 was to reflux 2-3 with methyl iodide and K2CO3

in acetone for two days following the literature method.63 However, the yield of this reaction was

no more than 30 % which was very low and inconvenient for the preparation of a starting

material. Another method was tried by stirring 2-3 with methyl iodide and K2CO3 in dry DIVF

for five days, which yielded 98 % of very clean product. The same method yielded successful









preparation of 2-7 by using octyl iodide with 65 % yield. For the preparation of 2-7 another

method was also tried by using sodium hydride'" instead of K2CO3 but unfortunately a mixture

of unknown products was obtained.

The last step of the synthesis of the lower side functionalized triphenoxymethane platform

is the reduction of the nitro groups of 2-6 and 2-7 to yield 3,3',3 "-methanetriyltri s(4-

methoxyaniline) (2-8) and 3,3',3"-methanetriyltris(4-(octyloxy)aniln (2-9) respectively as seen

in Scheme 2-1. This was a very challenging task. Various aromatic nitro group reduction

methods 63, 79-86 were used, and for each method different reaction conditions were applied by

changing the amount of the reagents, the temperature of the reaction, or the total time of the

reaction. However, in terms of the reaction safety, obtaining clean compound with high yield,

and the cost of the materials used, only one method s5 turned out to be successful in fulfilling all

these requirements. According to this method, 2-6 and 2-7 are refluxed with zinc dust and

calcium chloride dihydrate in ethanol overnight to obtain 2-8 and 2-9 in 50 % and 62 % yield,

respectively.

2.2.2 Synthesis of 6-(N, N-dialkylcarbamoyl)pyridine-2-carboxylic Acid

Two derivatives of 6-(N, N-di alkyl carb amoyl)pyri dine-2-carb oxyli c aci d were synthesized,

diethyl derivative 6-(N, N-diethylcarbamoyl)pyridine-2-carboxylic acid (2-4) and diisopropyl

derivative, (N, N-dii sopropyl carb amoyl)pyridine-2-carb oxyli c aci d (2-5). 2-4 87, 88, 89 was

prepared according to the published procedure. Similarly, 2-5, the isopropyl derivative of 2-4,

was successfully synthesized. In Scheme 2-2 the synthetic pathway for 2-5 is given. For the

synthesis of 2-5, 6-(methoxycarbonyl) picolinic acid is prepared as described in the literature.8

This molecule is reacted with thionyl chloride to make an acyl chloride, which is reacted with N,

N-diisopropyl amine. The final step is saponification of the methyl ester using KOH.









2.2.3 Synthesis of the Ligands

All the ligands were synthesized by using the coupling reagent; PyBOP.90 This reagent is

used for the condensation reactions between an amine and a carboxylic acid to form an amide

bond.

According to the general procedure for the coupling reactions, the amine derivative of the

triphenoxymethane platform was stirred with a 6-(N, N-di alkyl carb amoyl)pyri dine-2-carb oxyli c

acid derivative, PyBOP90, and N, N-diisopropyl amine in DMF at room temperature over night.

To the reaction mixture, 10 % HCI solution was added and stirred for an hour. The resulting

precipitate was dissolved in an organic solvent and washed first with 1 M HCI solution, then

with 1 M NaOH solution followed by brine solution. The organic layer was dried over anhydrous

sodium sulfate and filtered. The solvent was removed and the residue was dried.

Throughout our studies we worked with two different types of triphenoxymethane

platforms: upper side functionalized triphenoxymethane platform and lower side functionalized

triphenoxymethane platform. The ligands N2, N2', N2"-(3, 3', 3"-(6, 6', 6"-methanetriyltris(2, 4-

di-tert-butylbenzene-6, 1 -diyl)tri s(oxy))tri s(propane-3, 1-diyl))tris(N6, N6-diethylpyridine-2, 6-

dicarboxamide) (2-10), N2, N2', N2"-(2, 2', 2"-(6, 6', 6"-methanetriyltris(2,4-di-tert-

butylbenzene-6, 1 -diyl)tri s(oxy))tri s(ethane-2, 1 -diyl))tri s(N6, N6-diethylpyridine-2, 6-

dicarboxamide) (2-11), and N2, N2', N2"-(2, 2', 2"-(6, 6', 6"-methanetriyltri s(2, 4-di-tert-

butylbenzene-6, 1 -diyl)tri s(oxy))tri s(ethane-2, 1 -diyl))tri s(N6, N6-dii sopropylpyridine-2, 6-

dicarboxamide) (2-12) are the molecules made by using upper side functionalized

triphenoxymethane platform. The synthetic scheme for 2-10 and 2-11 are depicted in Scheme 2-

3. In Scheme 2-4 the synthetic pathway for 2-12 is shown.

The lower side functionalized triphenoxymethane platform was used to prepare N2, N2',

N2"-(3, 3', 3"-methanetriyltris(4-methoxybenzene-3, 1-diyl))tris(N6, N6-diethylpyridine-2, 6-









dicarboxamide) (2-13), N2, N2', N2"-(3, 3', 3 "-methanetriyltri s(4-methoxyb enzene-3, 1 -

diyl))tris(N6, N6-diisopropylpyridine-2, 6-dicarboxamide) (2-14), and N2, N2', N2"-(3, 3', 3"-

methanetriyltris(4-(octyloxy)benzene-3, 1-diyl))tris(N6, N6-diethylpyridine-2, 6-dicarboxamide)

(2-15) and N2, N2', N2"-(3, 3', 3 "-methanetriyltris(4-(octyloxy)benzene-3,1-diyl))tris(N6, N6-

diisopropylpyridine-2, 6-dicarboxamide) (2-16). In Scheme 2-5 the synthetic route for 2-13 and

2-15, and in Scheme 2-6 the synthetic route for 2-14 and 2-16 are depicted.

2.3 Conclusion

Nonadentate ligand systems bearing unsymmetrical pyridine-diamide moieties with both

upper- and lower-side functionalized triphenoxymethane platform derivatives have been

successfully synthesized and characterized. Their extraction behaviors with lanthanide (III)

cations in 1 M nitric acid solution will be discussed in detail in Chapter 3.

2.4 Experimental Section

2.4.1 General Considerations

All solvents and starting materials were purchased from Fisher Scientific and used without

purification unless otherwise stated. 2, 6-pyridine-dicarboxylic acid (Aldrich), 1-iodomethane

(Fisher), 1-iodooctane (Acros), potassium carbonate (anhydrous) (Fisher), Zn powder (Fisher),

CaCl2.2H20 (Acros), Ln(NO3)3.x H20 (Ln= La, Ce, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Er, Tm, Yb)

(Aldrich), PyBOP (benzotriazol-1 -yl)oxytripyrrolidinephosphonium hexafluorophosphate)

(Acros), N, N-diethylamine (Fisher), N, N-diisopropylamine (Fisher), N, N-diisopropylethyl

amine (Fisher), were used as obtained. Anhydrous DMF was used as received for reactions

requiring thi s solvent. 3, 3', 3 "-(6, 6', 6"-methanetriyltri s(2, 4-di-tert-butylbenzene-6, 1 -

diyl)tri s(oxy))tripropan-1 -amine, 2-176, 2, 2', 2"-(6, 6', 6"-methanetriyltri s(2, 4-di-tert-

butylbenzene-6, 1-diyl)tri s(oxy))triethanamine, 2-2 7, and 2, 2', 2"-methanetriyltri s(4-

nitrophenol), 2-363, were synthesized as reported. 6-(N, N-diethylcarbamoyl)pyridine-2-









carboxylic acid, 2-487, 88, 89 was prepared according to the published procedure. Following the

same procedure (N, N-dii sopropyl carb amoyl)pyri dine-2-carb oxyli c aci d 2-5, the dii sopropyl

derivative of 2-4, was successfully synthesized. All 1H NMR spectra were recorded on a Varian

VXR-300 or Mercury-300 spectrometer at 299.95 MHz. Elemental analysis was performed at the

University of Florida. The mass spectrometry analyses were performed on a Bruker APEX II 4.7

T Fourier Transform lon Cyclone Resonance mass spectrometer (Bruker Daltonics, Billerica,

MA).

2.4.2 Synthesis

Preparation of 6-(N, N-isopropylcarbamoyl)pyridine-2-carboxyli acid, 2-4: 6-

(methoxycarbonyl)picolinic acid was prepared as reported."' A solution of 6-

(methoxycarbonyl)picolinic acid (1.3 g, 7.8 mmol) was prepared with 100 mL dry CH2 12,

thionyl chloride (34. 16 g, 0.287 mmol) and 0. 1 mL of dry DMF and refluxed for 1 h. Volatiles

were removed under vacuum. The remaining solid was dissolved in 100 mL dry CH2 12 and N,

N-diisopropyl amine (7.265 g, 71.8 mmol) was added dropwise under N2 atmosphere. The

solution was refluxed for 90 minutes after which N, N-diisopropyl amine and CH2 12 were

removed under vacuum. The crude product was dissolved in 100 mL of CH2 12 and washed with

half saturated NH4C1 Solution. The aqueous phase was back-extracted with CH2 12 (3 x 100 mL).

The combined organic phases were washed with saturated KHCO3 Solution. After drying the

organic layer with Na2SO4, the solvent was removed and the residue was dried. The crude oily

brown residue was dissolved in 50 mL 1 M KOH solution and stirred for 10 minutes. The

aqueous phase was washed with chloroform (2 x 100 mL) and was then acidified with 25% HCI

solution to pH=2. A white compound precipitated out of the solution at pH=2. The product was

collected by filtration and dried. Yield: 1.40 g (78 %). 1H NMR (CDCl3) : 6 (ppm) 1.21 (6H, d,

3J= 6.6 Hz, CHCH3), 1.57 (6H, d, 3J = 6.9 Hz, CHCH3), 3.59 (1H, hept., 3J= 6.63 Hz. CHCH3),









3.73 (1H, hept., 3J= 6.8 CHCH3 ), 7.73 (1H, dd, 3J= 7.8 Hz, 4J= 0.9 Hz, Py-H), 8.05 (1H, t, 3J

= 7.8 Hz, Py-H), 8.25 (1H, dd, 3J= 6.9 Hz, 4J= 0.9 Hz, Py-H). Calculated for C13H18N203: C

62.3 8, N 1 1.19, H 7.25. Found: C 62. 13, N 1 1.06, H 7.3 5. ESI-FT-ICR-MS m/z 273.1225 for

[C13HlsN203+Na]+. Expected: 273.1210.

Preparation of tris(2-methoxy-5-nitrophenyl)methane, 2-6: A mixture of 2, 2', 2"-

methanetriyltris(4-nitrophenol), 2-3, (9.30 g, 21.76 mmol), anhydrous K2CO3 (15.04 g, 108.8

mmol), CH3I (15.45 g, 108.8 mmol) and 125 mL of anhydrous DMF was stirred for Hyve days at

room temperature. 200 mL of water was added and the mixture was stirred for 1 h. The

precipitate was collected by filtration, washed with water and dried. Yield: 10.05 g, (98 %). 1H

NMR (CDCl3): 6 (ppm) 3.84 (9H, s, OCH3), 6.25 (1H, CH), 6.99 (3H, d, 3J = 9.0 Hz, Ar-H),

7.66 (3H, d, 4J= 2.7 Hz, Ar-H), 8.25 (3H, dd, 3J= 9.2 Hz, 4J= 2.85 Hz, Ar-H). Calculated for

C22H19N309: C 56.29, N 8.95, H 4.08; Found: C 56.69, N 8.57, H 3.91.

Preparation of tris(5-nitro-2-(octyloxy)phenyl)methane, 2-7: Similar synthetic

methodology was applied to the synthesi s of 2-7. 2, 2', 2"-methanetriyltri s(4-nitrophenol), 2-3,

(5.0 g, 11.7 mmol), anhydrous K2CO3 (8.09 g, 58.5 mmol), 1-iodooctane (14.05 g, 58.5 mmol)

and 60 mL of anhydrous DMF were stirred for Hyve days at room temperature. 200 mL of water

was added and the mixture was stirred for 1 h. The oily product was separated from the aqueous

part. After washing the thick oil several times with water (3 x 100 mL), it was dissolved in

CH2C 2. The organic solution was washed with water (3 x 100 mL), dried over Na2SO4, and the

solvent was removed under vacuum. The resulting thick oil was stirred in 250 mL of pentane for

3 hours. The pure product was filtered from pentane solution as solid. Yield: 5.80 g, (65 %). 1H

NMR (CDCl3): 6 (ppm) 0.85 (9H, t, 3J= 6.9 Hz, OCH2CH2(CH2)5CH3), 1.22 (30H, br,

overlapping signal, OCH2CH2 (CH2)5CH3), 1.55 (6H, p, 3J = 5.5 Hz, OCH2CHz(CH2)5CH3), 3.94









(6H, t, 3J= 6.2 Hz, OCH2CH2(CH2)5CH3), 6.24 (1H, s, CH), 6.91 (3H, d, 3J= 9.0 Hz, Ar-H),

7.69 (3H, d, 4J= 2.7 Hz, Ar-H), 8.19 (3H, dd, 3J= 9.2 Hz, 4J= 2.9 Hz, Ar-H). Calculated for

C43H61N309: C 67.69, N 5.50, H 8.05. Found C 67.60, N 5.49, H 8.21.

Preparation of 3,3',3"-methanetriyltris(4-methoxyanilin) 2-8 This molecule was

prepared following a literature procedure with a slight modification." Tris(2-methoxy-5-

nitrophenyl)methane, 2-6 (1.0 g, 2. 13 mmol), was dissolved in 125 mL of absolute ethanol. Zn

dust (14.46 g, 221 mmol) was added to the solution. While stirring the mixture, CaCl2.2H20

(1.156 g, 7.86 mmol) was dissolved in minimum volume of water and added slowly to the

mixture. The final mixture was refluxed overnight. The solution was then filtered and the solids

were washed with ethanol. Saturated NaHCO3 Solution (200 mL) was added to the filtrate, which

was then stirred for 30 minutes. The solution was extracted with CH2 12 (2 x 200 mL). The

organic layer was washed with water (3 x 200 mL), dried over Na2SO4, and the solvent was

removed to give 2-8 as solid. Yield: 0.40 g, (50 %). 1H NMR (CD3CN): 6 (ppm) 3.56 (9H, s,

CH3), 3.66 (6H, br, Ar-N\H2), 6. 12 (3H, d, 4J = 3.0 Hz, Ar-H), 6. 13 (1H, s, CH), 6.44 (3H, dd, 3J

= 8.3 Hz, 4J= 2.9 Hz, Ar-H), 6.69 (3H, d, 3J = 8.7 Hz, Ar-H). Calculated for C22H25N303:

69.64, N 11.07, H 6.64; Found: C 69.54, N 10.85, H 6.78.

Preparation of 3, 3', 3"-methanetriyltris(4-(octyloxy)aniline, 2-9: The synthetic route

for 2-9 was very similar to that of 2-8 with the exception that higher mole ratio of Zn dust and

CaCl2.2H20 were used. After preparing a solution of tri s(5 -nitro-2-(octyloxy)phenyl)methane, 2-

7, (1.0 g, 1.309 mmol), Zn dust (10.27 g, 157 mmol) in 125 mL of ethanol, CaCl2.2H20 (1.32 g,

8.98 mmol) solution, prepared in minimum amount of water, was added dropwise. The resulting

solution was refluxed over night. The solution was filtered and washed with ethanol. A 200 ml

saturated solution of NaHCO3 WAS prepared and added to the filtrate. The final solution was









stirred for 30 minutes. The solution was extracted with CH2C 2 (2 x 200 mL). The organic layer

was extracted with water (3 x 200 mL) and dried over Na2SO4. The solvent was removed to

dryness to give 2-9. Yield: 0.55 g, (62 %). 1H NMR (CD3CN): 6 (ppm) 0.87 (9H, 3J = 6.8 Hz,

OCH2CH2(CH2)5CH3), 1.26 (30H, br, two broad overlapping peaks OCH2CH2 (CH2)5CH3),

1.54 (6H, br, OCH2CHz(CH2)5CH3), 3.63 (6H, br Ar-NH2), 3.71 (6H, t, 3J = 6.5 Hz,

OCHzCH2(CH2)5CH3), 6.10 (3H, d, 4J= 3.0 Hz, Ar-H), 6.28 (1H, s, CH), 6.39 (3H, dd, 3J= 8.4

Hz, 4J= 2.7 Hz, Ar-H), 6.63 (3H, d, 3J = 8.7 Hz, Ar-H).

Preparation of N2, N2', N2"-(3, 3', 3"-(6, 6', 6"-methanetriyltris(2, 4-di-tert-

butylbenzene-6, 1-diyl)tris(oxy))tris(propane-3, 1-diyl))tris(N6, N6-diethylpyridine-2, 6-

dicarboxamide), 2-10: A mixture of 6-(N, N-diethylcarbamoyl)pyridine-2-carboxylic acid, 2-8,

(0. 93 g, 4.13 mmol), PyBOP90 ( 2.39 g, 5,57 mmol), N, N-diisopropylethylamine (1.38 mL, 8.33

mmol) and 3, 3', 3"-(6, 6', 6"-methanetriyltri s(2, 4-di-tert-butylbenzene-6, 1-

diyl)tri s(oxy))tripropan-1 -amine, 2-1, 1.00 g, 1.25 mmol) was stirred in anhydrous DMF (25

mL) at room temperature for 22 hours. 100 mL of 10% HCI solution was added and the mixture

was stirred for 1 hour. The resulting precipitate was isolated by filtration and then dissolved in

ether. The ether solution was washed with 1 M HCI solution (3 x 200 mL), 1 M NaOH (3 x 200

mL), and finally once with 200 mL of brine solution. The organic layer was dried over Na2SO4

and concentrated. The resultant oily residue was treated with a few milliliters of pentane and a

few drops of acetone and the product precipitated as a white solid. Yield: 0.98 g, (56 %).

Diffusion of pentane into an ether solution of the ligand gave crystals suitable for X-ray analysis.

1H NMR (CDCl3) : 6 (ppm) 1.12 (9H, t, 3J= 7.2 Hz, CONCH2CH3), 1.18-1.23 (coinciding

peaks 9H, t, CONCH2CH3 with 27H, s, Ar-(CCH3)3) ,1.34 (27, s, Ar-C(CH3)3), 2. 16 (6H, p, 3J

6.9 Hz, Ar-O(CH2CH2CH2)NH), 3.25 (6H, q, 3J = 7.2 Hz, CONCH2CH3 ), 3.46 (6H, q, 3J = 7.2









Hz, CONCH2CH3), 3.62 (6H, t, 3J = 6. 1 Hz, Ar-O(CHZCH2CH2)N\H), 3.73 (6H, q, 3J=7.3 Hz,

Ar-O(CH2CH2CH2)NH), 6.44 (1H, s, CH), 7. 17 (6H, s, Ar-H), 7.64 (3H, dd, 3J= 7.6 Hz, 4J = 1.2

Hz, Py-H), 7.90 (3H, t, 3J = 7.7 Hz, Py-H), 8. 17 (3H, dd, 3J= 7.7 Hz, 4J = 1.0 Hz, Py-H), 8.24

(3H, t, 3J= 5.7 Hz, Ar-O(CH2CH2CH2)NH). Calculated for CssH121N909: C 72.26, N 8.92, H

8.63; Found: C 72.02, N 8.77, H 8.86. ESI-FT-ICR-MS m/z 1412.9371 for [CssH121N909+H] .

Expected: 1412.9321.

Preparation of N2, N2', N2"-(2, 2', 2"-(6, 6', 6"-methanetriyltris(2, 4-di-tert-

butylbenzene-6, 1-diyl)tris(oxy))tris(ethane-2, 1-diyl))tris(N6, N6-diethylpyridine-2, 6-

dicarboxamide), 2-11: A solution of 6-(N, N-diethylcarbamoyl)pyridine-2-carboxylic acid, 2-8

(0.98 g, 4.39 mmol), 2, 2', 2"-(6, 6', 6"-methanetriyltris(2, 4-di-tert-butylbenzene-6, 1-

diyl)tris(oxy))triethanamine, 2-2, (1.00 g, 1.32 mmol), PyBOP90 (2.51 g, 4.83 mmol) and N, N-

diisopropylethylamine (1.45 mL, 8.79 mmol) was prepared in 25 mL anhydrous DMF and was

stirred for 22 hours at room temperature. 100 mL of 10% HCI solution was prepared and added

to the mixture. The resulting solution was stirred for 1 hour. The precipitate formed after the

addition of HCI solution was filtered and then dissolved in ether. The ether solution was

extracted with 1 M HCI solution (3 x 200 mL), 1 M NaOH (3 x 200 mL), and with 200 mL of

brine solution. The ether layer was dried over Na2SO4 and concentrated. The oily residue was

treated with pentane to give pure, white product. Yield: 0.80 g, (44 %). 1H NMR (CDCl3): 6

(ppm) 1.05 (9H, t, 3J= 7.0 Hz, CONCH2CH3), 1.14 (9H, t, 3J= 7.2 Hz CONCH2CH3), 1.22

(27H, s, Ar-(CCH3)3), 1.26 (27H, s, Ar-C(CH3)3), 3.32 (6H, q, 3J = 7.2 Hz, CONCH2CH3 ), 3.45

(6H, q, 3J= 7.1 Hz, CONCH2CH3), 3.69 (6H, v. br. s. OCH2CH2), 4.31 (6H, v. br. s. OCH2CH2),

6.66 (1H, s, CH), 7. 17 (3H, d, 4J = 2.3 Hz, Ar-H), 7.33 (3H, d, 4J = 2.6 Hz, Ar-H), 7.66 (3H,

dd, 3J= 7.9 Hz, 4J = 1.2 Hz, Py-H), 7.91 (3H, t, 3J = 7.9 Hz, Py-H), 8.27 (3H, dd, 3J = 7.7 Hz, 4J









= 1.0 Hz, Py-H), 8.52 (3H, t, 3J= 6.0, Ar-O(CH2CH2CH2)NH).Calculated for C82H115N909: C

71.84, N 9.20, H 8.46; Found: C 71.37, N 8.93, H 8.71. ESI-FT-ICR-MS m/z 1369.8822 for

[C82H115N909] Expected: 1369.8818.

Preparation of N2, N2', N2"-(2, 2', 2"-(6, 6', 6"-methanetriyltris(2, 4-di-tert-

butylbenzene-6, 1-diyl)tris(oxy))tris(ethane-2, 1-diyl))tris(N6, N6-diisopropylpyridine-2, 6-

dicarboxamide), 2-12: Starting with 6-(N, N-dii sopropyl carb amoyl)pyri dine-2-carb oxyli c aci d,

2-9, (1.10 g, 4.40 mmol), 2, 2', 2"-(6, 6', 6"-methanetriyltris(2, 4-di-tert-butylbenzene-6, 1-

diyl)tris(oxy))triethanamine, 2-2, (1.00 g, 1.32 mmol), PyBOP90 (2.52 g, 4.83 mmol) and N, N-

diisopropylethylamine (1.45 mL, 8.79 mmol) a solution was prepared in 25 mL anhydrous DMF.

After stirring the solution for 22 hours at room temperature, 100 mL of 10% HCI solution was

added. The final solution was stirred for 1 hour. A precipitate formed after the addition of HCI

solution which was then filtered and dissolved in ethyl acetate. The ethyl acetate solution was

washed with 1 M HCI solution (3 x 200 mL), 1 M NaOH (3 x 200 mL), and finally with 200 mL

of brine solution. After drying the ethyl acetate layer over Na2SO4, the solvent was removed. The

oily residue was treated with pentane to give pure, white solid product, 2-12. Yield: 1.24 g, (65

%). 1H NMR (CDCl3): 6 (ppm) 1.09 (18H, d, 3J= 6.6 Hz, CONCH(CH3)CH3), 1.18 (27H, s, Ar-

C(CH3>3), 1.22 (27H, s, Ar-C(CH3>3), 1.41 ((18H, br, CONCH(CH,)CH3), 3 .42 (3H, hept., 3J

4.4 Hz, CONCH(CH3)CH3), 3.56 (6H, br, Ar-O(CH2CH2)NH), 3.73 (3H, hept., 3J = 5.8 Hz,

CONCH(CH3)CH3), 4.39 (6H, br, Ar-O(CH2CH2)NH), 6.62, (1H, s, CH), 7. 13 (3H, d, 4J = 2.4

Hz, Ar-H), 7.25 (3H, 4J = 2.4 Hz, Ar-H), 7.21 (3H, dd, 3J = 7.7 Hz, 4J= 1.1 Hz, Py-H), 7.87 (3H,

t, 3J = 7.8 Hz, Py-H), 8.23 (3H, dd, 3J= 7.7 Hz, 4J= 1.1 Hz, Py-H), 8.44 (3H, t, 3J = 6.2 Hz, Ar-

O(CH2CH2)NH). Calculated for C88H127N909: C 72.64, N 8.66, H 8.80; Found: C 72.40, N 8.52,

H 9.02. ESI-FT-ICR-MS m/z (CssH127N909+H) = 1455.9983. Expected: 1454.9829.









Preparation of N2, N2', N2"-(3, 3', 3"-methanetriyltris(4-methoxybenzene-3, 1-

diyl))tris(N6, N6-diethylpyridine-2, 6-dicarboxamide), 2-13: The mixture of 3, 3', 3"-

methanetriyltris(4-methoxyaniline), 2-6, (1.69 g, 4.45 mmol), 6-(N, N-

diethylcarbamoyl)pyridine-2-carboxylic acid, 2-8, ( 3.30 g, 14.78 mmol), PyBOP90 (8.51 g,

20.17 mmol), N, N-diisopropylethylamine (4.9 mL, 29.57 mmol) was dissolved in 25 mL

anhydrous DMF. The solution was stirred at room temperature for 22 hours. To this solution, 100

mL of 10% HCI solution was added. After stirring for 1 hour, the precipitate that formed after

the addition of HCI solution was removed by filtration and dissolved in ethyl acetate. Following

the extraction of the ethyl acetate solution by 1 M HCI solution (3 x 200 mL), 1 M NaOH (3 x

200 mL), and with 200 mL of brine solution, the organic layer was dried over Na2SO4. After

removing the solvent, the solid product was washed with methanol then with an acetone-pentane

mixture, and filtered to give pure solid product, 2-13. Yield: 1.88g, (43 %). 1H NMR (CDCl3): 6

(ppm) 1.04 (9H, t, 3J = 6.9 Hz, NCH2CH3), 1.10 (9H, t, 3J = 7.2 Hz, NCH2CH3), 3.20 (6H, q, 3J

= 6.9 Hz, NCH2CH3), 3.39 (6H, q, 3J= 7.1 Hz, NCH2CH3), 3.71 (9H, s, Ar-OCH3), 6.38 (1H, s,

CH), 6.61 (3H, d, 3J= 2.4 Hz, Ar-H), 6.91 (3H, d, 3J = 9.0 Hz, Ar-H), 7.71 (3H, dd, 3J = 7.8 Hz,

4J= 1.2 Hz, Py-H), 7.94 (3H, t, 3J = 8.0 Hz, Py-H), 8.13 (3H, dd, 3J = 8.9, 4J = 2.6 Hz, Ar-H),

8.25 (3H, dd, 3J= 7.7 Hz, 4J = 1.1 Hz, Py-H), 9.56 (3H, s, Ar-NH). ESI-FT-ICR-MS m/z

(C55H61N909 + H) = 992.4719. Expected: 992.4665.

Preparation of N2, N2', N2"-(3, 3', 3"-methanetriyltris(4-methoxybenzene-3, 1-

diyl))tris(N6, N6-diisopropylpyridine-2, 6-dicarboxamide), 2-14: A mixture of 3, 3', 3"-

methanetriyltris(4-methoxyaniline), 2-6 (0.59 g, 1.56 mmol), 6-(N, N-

dii sopropyl carb amoyl)pyri dine-2-carb oxylic acid, 2-9, ( 1.3 g, 5.19 mmol), PyB OP90 ( 2.92 g,

6.92 mmol), N, N-diisopropylethylamine (1.71 mL, 10.32 mmol) in 25 mL anhydrous DMF was









stirred at room temperature for 22 hours. A 100 mL of 10% HCI solution was prepared and

added to the solution. The resulting solution was stirred for 1 hour and filtered to separate the

precipitate formed after the addition of HCI solution. The precipitate was dissolved in

dichloromethane and extracted by 1 M HCI solution (3 x 200 mL), 1 M NaOH (3 x 200 mL), and

with 200 mL of brine solution. After drying the organic layer over Na2SO4, dichloromethane was

removed and the solid residue was washed with methanol to give 2-14 as pure solid. Yield: 0.54

g, (32 %). Diffusion of pentane into a THF solution of the ligand gave crystals suitable for X-ray

analysis. 1H NMR (CDCl3): 6 (ppm) 1.00 (18H, d, 3J = 6.6 Hz, CONCH(CH3)CH3), 1.34 (18H,

d, 3J = 6.6 Hz, CONCH(CH3)CH3), 3.36 (3H, hept., 3J = 6.5 Hz, CONCH(CH3)CH3), 3.71 (9H,

s, Ar-OCH3), 3.85 (3H, hept., 3J = 7.2 Hz, CONCH(CH3)CH3), 6.34 (1H, s, CH), 6.50 (3H, d, 3J

= 2.7 Hz, Ar-H), 6.90 (3H, d, 3J= 9.0 Hz, Ar-H), 7.65 (3H, dd, 3J = 7.8 Hz, 4J= 1.2 Hz, Py-H),

7.93 (3H, t, 3J= 7.8 Hz, Py-H), 8. 18 (3H, dd, 3J= 8.9 Hz, 4J = 2.6. Hz, Ar-H), 8.22, (3H, dd, 3J

8.1 Hz, 4J = 0.9 Hz, Py-H), 9.61 (3H, s, Ar-N\H). ESI-FT-ICR-MS m/z (C61H73N909+H)+ =

1076.5643. Expected: 1076.5604.

Preparation of N2, N2', N2"-(3, 3', 3"-methanetriyltris(4-(octyloxy)benzene-3 1-

diyl))tris(N6, N6-diethylpyridine-2, 6-dicarboxamide), 2-15: A mixture of 3, 3', 3"-

methanetriyltris(4-(octyloxy)aniline, 2-7, (0.97 g 1.44 mmol), 6-(N, N-

diethylcarbamoyl)pyridine-2-carboxylic acid, 2-8, (0.97 g, 4.36 mmol), PyBOP90 (2.50 g, 5.93

mmol), and N, N-diisopropylethylamine (1.44 mL, 8.69 mmol) were stirred in 25 mL anhydrous

DMF for 22 hours at room temperature. After the addition of 100 mL of 10% HCI solution to the

reaction mixture, the resulting mixture was stirred for 1 hour. In order to separate the precipitate

formed after the addition of HCI solution, the solution was filtered. The precipitate was dissolved

in dichloromethane which was then extracted by 1 M HCI solution (3 x 200 mL), 1 M NaOH (3









x 200 mL), and with 200 mL of brine solution. The organic layer was dried over Na2SO4 and the

solvent was removed. The residue was washed with pentane to give brown solid. The brown

solid was further purified by column chromatography by using basic alumina with 4% methanol:

ethyl acetate solution. Yield: 0.92 g, (56 %). 1H NMR (CDCl3): 6 (ppm) 0.83 (9H, t, 3J= 6.9 Hz,

OCH2CH2(CH2)5CH3), 1.06 (18 H, multiple coinciding with the broad peak at 1.18, NCH2CH3),

1.18 (30H, br, overlapping with the multiplets at 1.06, OCH2CzCH2(5CH3)C3, 1.72 (6H, br,

OCH2CHz(CH2)5CH3), 3.21 (6H, q, 3J= 7.2 Hz, NCH2CH3), 3.38 (6H, q, 3J = 7.2 Hz,

NCH2CH3), 3.84 (6H, t, 3J= 6.4 Hz, OCHzCH2(CH2)5CH3), 6.49 (1H, s, CH), 6.58 (3H, d, 3J

3.0 Hz, Ar-H), 6.85 (3H, d, 3J= 8.7 Hz, Ar-H), 7.72 (3H, dd, 3J = 7.8 Hz, 4J = 0.9 Hz, Py-H),

7.94 (3H, t, 3J= 7.8 Hz, Py-H), 8. 11 (3H, dd, 3J= 9.0 Hz, 4J = 2.4 Hz, Ar-H), 8.30 (3H, dd, 3J

8.1 Hz, 4J = 1.0 Hz, Py-H), 9.55 (3H, s, Ar-N\H). ESI-FT-ICR-MS m/z (C76H103N909+H)+ =

1286.8074. Expected: 1286.7951.

Preparation of N2, N2', N2"-(3, 3', 3"-methanetriyltris(4-(octyloxy)benzene-3 1-

diyl))tris(N6, N6-diisopropylpyridine-2, 6-dicarboxamide), 2-16: Synthesis of this ligand was

also carried out with the common method of the coupling reagent PyBOP.90 A solution with 3,

3', 3"-methanetriyltri s(4-(octyloxy)aniline, 2-7, (1.22 g, 1.60 mmol), 6-(N, N-

dii sopropyl carb amoyl)pyri dine-2-carb oxylic acid, 2-9, ( 1.3 7 g, 5.47 mmol), PyB OP90 (3. 14 g,

7.45 mmol), and N, N-diisopropylethylamine (1.81 mL, 10.92 mmol) was prepared in 25 mL

anhydrous DMF and was stirred for 22 hours at room temperature. After adding 100 mL of 10 %

HCI solution, the final solution was stirred for 1 hour. During stirring in acid solution, a

precipitate formed which was later filtered and dissolved in dichloromethane. The organic layer

was washed with 1 M HCI solution (3 x 200 mL), 1 M NaOH (3 x 200 mL), and with 200 mL of

brine solution. After the organic layer was dried over Na2SO4, the solvent was removed and the









residue was washed with pentane and dried to give 2-16 as brown solid. Yield: 1.49 g, (68 %).

1H NMR (CDCl3): 6 (ppm) 0.83 ( 9H, t, 3J = 6.9 Hz, Ar-O(CH2)7CH3), 1.00 (18H, d, 3J = 6.9

Hz, CONCH(CH3)CH3), 1.17 (30H, br, OCH2CH2(CH2)5CH3), 1.33 (18H, d, 3J= 6.3 Hz,

CONCH(CH3)CH3), 1.79 (6H, br, OCH2CHz(CH2)5CH3), 3.35 (3H, hept., 3J = 6.4 Hz,

CONCH(CH3)CH3), 3.56 (3H, br, hept., CONCH(CH3)CH3), 3.83 (6H, t,3J= 6.2 Hz, Ar-

OCHz(CH2)6CH3) 6.46 (1H, s, CH), 6.48 (3H, d, 3J= 2.7 Hz, Ar-H), 6.84 (3H, d, 3J= 9.0 Hz,

Ar-H), 7.65 (3H, dd, 3J= 7.8 Hz, 4J = 1.0 Hz, Py-H), 7.93 (3H, t, 3J = 7.8 Hz, Py-H), 8.17 (3H,

dd, 3J= 8.6 Hz, 4J = 2.6 Hz, Ar-H), 8.22, (3H, dd, 3J = 7.9 Hz, 4J = 1.0 Hz, Py-H), 9.60 (3H, s,

Ar-NH).






O O






N




N 03 NO 3


B C

Figure 2-1 Structures of A) N, N, N', N' -tetraethylpyridine-2, 6-dicarboxamide and its tripodal
derivatives with B) TREN and C) Me-TRPN.













(H2C)6 /CH2)6
O O


~'o'


f

"`0,


"`N


Figure 2-2 Structures of some recently studied DPA ligands.A) tetra-n-butyl DPa, B) N,N'-
diheptyl DPA, C) tetra-i-butyl DPA, D) N, N' -diethyl-N.N'-di(p-tolyl) DPA, E)
N,N' -diphenyl-N,N' dimethyl DPA.







































1. SOCl2, DMF, CH2 12
2. N, N-diisopropylamine
CH2 12
3. 1 M KOH


OR




NO2


Zn, CaCl2.2H20

EtOH
reflux overnight


5 RI, 5 K2CO3

Dry DMF, stir 5 days


NH2


(R= methyl, octyl) 26(=Mty)
2-7 (R= Octyl)


2-8 (R= Methyl)
2-9 (R=0ctyl)


Scheme 2-1 Reaction scheme for the synthesis of 2-6, 2-7, 2-8 and 2-9.


~N7


MeO N OH
O O


6-(methoxyca rbonylI)
picolinic acid

Scheme 2-2 Synthetic scheme for 2-5.


OH




NO2

2-3

















N~ \


HO Na N
2-4


n= 1, 2


n=1, 2


Pybop, N, N-diisopropylethylamine
Dry DMF
stir over night


2-1 (n= 2)
2-2 (n= 1)


2-10 (n= 2)
2-11 (n=1)


Scheme 2-3 Synthesis of 2-10 and 2-11i.


~NH2


HO~K~c

2-5


Pybop, N, N-diisopropylethylamine
Dry DMF
stir over night

2-2 (n =1 )



Scheme 2-4 Synthetic scheme for 2-12.


2-12












HO"~ N 3
NH
2-4 O
Pybop, N, N-diisopropylethy lami ne \
Dry DMFN
Stir overn ight

O`


2-8 (R= Methyl)
2-9 (R= Octy I)


2-13 R= methyl
2-15 R= octyl


Scheme 2-5 Synthesis of 2-13 and 2-15.


NH


OP

N


Pybop, N, N-diisopropylethylamine
Dry DMF
Stir ove rn ight


2-8 (R= Methyl)
2-9 (R=0ctyl)


2-1 4 (R=M ethyl)
2-16 (R=0ctyl)


Scheme 2-6 Synthesis of 2-14 and 2-16.


OR



NH 2


OR



NH 2









CHAPTER 3
EXTRACTION EFFICIENCIES OF C3-SYMMETRIC NONADENTATE LIGAND SYSTEMS
WITH LANTHANIDE (III) CATIONS INT ACIDIC MEDIUM

3.1 Introduction

Treatment of highly radioactive nuclear waste is a challenging scientific problem. The

reason that makes it so challenging is that highly acidic waste contains chemically similar

trivalent lanthanide and actinide cations as a mixture which makes the transmutation of the

actinides impossible.

Scientific research studies have been focused on developing new methods for the

separation of these metal ions. Although numerous extractants have been developed for the

selective separation of actinides from lanthanides in highly acidic media, none of the extractants

has been suitable for industrial processing. In order to be applicable for industrial processing a

ligand must be incinerable, stable both to acidic and highly radioactive conditions, and be able to

extract actinides selectively and quantitatively from nuclear waste. The extractants that have

been studied so far lack one or two of these requirements for the nuclear waste treatment.

Since water and/or acid coordination and the solubility of the metal complex in the organic

phase are also important factors in extractions, it is not possible to predict how efficient the

target ligand will be without doing the extraction experiments. As a result, the research towards a

proper ligand is a trial and error process involving extraction experiments with each ligand

prepared.

Extraction experiments are performed in acidic solutions containing actinides and/or

lanthanides that mimic nuclear waste solutions. The extractant is dissolved in an immiscible

organic solvent and is expected to react with the metal ions when in contact with the aqueous

phase and in this way pull the metals into the organic layer.









In the previous chapter, C3-Symmetric nonadentate ligand systems with asymmetric DPA

groups bearing both pyridine and diamide groups were introduced. The goal of this ligand

design was to take advantage of both the pyridine and diamide groups for their individual

extraction properties reported in the literature in addition to the advantage of reorganization

imported by introducing them to the triphenoxymethane platform. In this chapter the results of

the extraction experiments with all the prepared ligands are discussed. The effect of different

types of triphenoxymethane platforms were also analyzed for the extraction experiments. NMR

scale extraction experiments were performed with 2-13 and the results will be presented for this

experiment. Two metal complexes of 2-10 were prepared and the crystal structures of these

complexes will be depicted as well as solid state structures of 2-10, 2-13, and 2-14. Extraction

experiments were performed in three different solvents for each ligand. In order to see the effect

of a synergist, extraction experiments were also performed with COSAN solutions. The results

with and without COSAN will also be discussed in this chapter.

3.2 Results and Discussion

3.2.1 Extraction Experiments

Extraction experiments were performed according to the given procedure.n For the

extraction experiments standard solutions of 1x10-4 M lanthanide (III) were prepared in 1 M

nitric acid solution. A total of eleven cations from the lanthanide series were used for the

extractions which are La, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Er, Tm, and Yb. Their concentrations were

determined by UV-Vis spectroscopy at 655 nm with Arsenazo (III) salt. Arsenazo (III) salt is a

dye with which lanthanide (III) ions form complexes at 2.8 pH. These complexes have an

absorbance at 655 nm enabling determination of the concentrations of the complexes. For the

extraction experiments not involving CO SAN, lx10-3 M ligand solutions were prepared in either

CH2C 2 Or 1-octanol. Extraction experiments involving CO SAN required 1, 2-dichloroethane









because CO SAN is obtained as cesium salt (Cs(COSAN), hexachlorobis (1, 2dicarbollide)

cobaltate cesium salt) which is soluble in this solvent. To increase the solubility of CO SAN for

the extraction experiments, the cesium CO SAN salt must be converted in HCOSAN. For this

purpose, the required amount of Cs (COSAN) was dissolved in 1, 2-dichloroethane, and this

solution was extracted repeatedly with 3 M H2SO4 Solution to produce HCOSAN. Once

HCOSAN solution was prepared, the required amount of ligand was dissolved in this solution to

prepare the HCOSAN-ligand mixture.

Equal volumes of the organic phase and the aqueous phase were shaken together for 16

hours. After phase separation, Arsenazo (III) solutions of the aqueous layer were prepared and

the concentrations of the remaining lanthanides in the aqueous layer were determined. The

extraction percentages were calculated with the formula: %E = [(Al A)/ (Al- Ao)] x 100. In this

equation Ao is the absorbance of 1 M nitric acid solution without any metal, Al is the absorbance

of the solution before extraction and A is the absorption after the extraction. The distribution

ratios of the metals were calculated as well with the following formula: D= E Morg Maq. The

extraction experiments were repeated three times to test their reproducibility. All the extraction

data for each of the ligands is included in Appendix A.

3.2.2.1 Extraction properties of the ligands with the upper side functionalized
triphenoxymethane platform

Two different derivatives of the upper side functionalized triphenoxymethane platform

were used for the synthesis of the ligands. The first derivative, 2-1, is more flexible with three

carbon linkers between the platform and the coordination site and the second derivative, 2-2, is

more rigid having two carbon linkers between the platform and the binding site. By using these

platforms, ligands 2-10, 2-11 and 2-12 were synthesized. Both 2-10 and 2-11 have ethyl

substituents. On the other hand 2-12, synthesized with the two carbon linker triphenoxymethane









derivative, has isopropyl substituents. The isopropyl derivative was prepared to increase the

lipophilicity of the ligand. In this way the solubilities of the complexes formed during the

extractions were expected to increase in the organic phase.

All these ligands showed similar extraction behaviors. They moderately extracted the

lanthanides in CH2 12 Solution. Experiments were performed with 1x10-3 M ligand and 1x10-4 M

Ln concentration. Performing an experiment with 100: 1 ratio of 2-10 to Ln (III) did not make

any change and the extraction was still poor. To observe the solvent effect, the same extractions

with 10: 1 ligand to metal ratio were repeated in 1-octanol with 2-10. However, the extraction

percent was approximately zero in this solvent. These experiments confirmed that these

molecules did not extract metals from acidic solution efficiently when used alone.

To investigate the effect of a synergist, an extraction experiment was performed with

ligand 2-10 using CO SAN in 1, 2-dichloroethane solution. In this experiment metal to CO SAN

to ligand ratios were 1: 10: 100. Unfortunately, there was not any extraction with this ligand even

in the presence of COSAN.

3.2.2.2 Extraction properties of the ligands with the lower side functionalized
triphenoxymethane platform

In the literature it is reported that extraction properties of the calixarenes change depending

on the functionalization of the upper (wide) or lower (narrow) rim.2 The extraction performances

of wide rim functionalized calixarenes with CMPO groups were better than narrow rim

functionalized calixarenes. The reason for this difference was believed to be the greater

flexibility of the CMPO moieties provided by the wide rim when compared to the narrow rim.2

Similarly, for the triphenoxymethane platform with CMPO ligand, extraction studies with both

upper side functionalized" and lower side functionalized 63 platforms were performed. To see

the effect of using different type of platform, two different derivatives of the lower side









functionalized triphenoxymethane platforms were prepared. One of them has methyl protecting

group and the other one has the octyl protecting group. The second one is more liphophilic than

the first. For each of these platforms, both ethyl and isopropyl derivatives of the ligands were

synthesized. Ligands 2-13 and 2-15 are the ethyl derivatives of the methyl protected and octyl

protected platforms, respectively. Ligands 2-14 and 2-16 are the isopropyl derivatives of methyl

and octyl protected platforms. The liphopilicity of the ligands increases in the order 2-13< 2-14<

2-15 <2-16.

The extraction experiments revealed that none of these ligands shows any extractability

towards lanthanide (III) ions when used alone with 10: 1 ligand to metal ratio in CH2C 2. They

showed very similar behaviors to the upper side functionalized ligands. However, as indicated

previously, Smirnov et al. also observed the same behavior with Daps.

Ligands 2-15 and 2-16 are the bulkiest ligands which makes them the most liphophilic

ligands in the series. Extraction experiments with these two ligands were performed in 1-octanol

solution, in hopes of making the extracted metal complexes soluble in the organic phase to

achieve better results. However, none of the ligands showed any extraction in 1-octanol.

As none of the ligands extracted lanthanide (III) ions from acidic solutions when used

alone, extraction experiments with the synergist COSAN were performed. According the

experiments performed with CO SAN in 1, 2-dichloroethane, except for 2-16, all the lower side

functionalized ligands showed extractability. The efficiency of the extractions depends on the

ratios of the CO SAN: ligand: metal. 2-13 and 2-15 extract lanthanides 100 % without selectivity

with 30: 10: 1 ratio of CO SAN: ligand: metal. However, when the ratio is 10: 1: 1, the extraction

efficiencies of the ligands tend to drop. In the extraction data that are given for 2-13, 2-14 and 2-

15 for lx10-3 M COSAN, lx10-4 M ligand and 1x10-4 M Ln the distribution ratios for 2-13 show










slight selectivity between the lighter and the heavier lanthanides. The distribution ratios of 2-14

are similar to that of 2-13, but the selectivity is apparently better. In the case of 2-15, there is

moderate extraction even in the presence of COSAN with the same concentration. Extraction

experiments with the same conditions were performed for 2-16 as well, but this ligand did not

show any extraction efficiency.

These results indicate that the extraction performances of the ligands strongly depend on

the amount of the synergist used and the type of the lower side functionalized triphenoxymethane

platform. The platform with the methyl protecting group works efficiently both with the ethyl

derivative, 2-13, and the isopropyl derivative, 2-14. However, with the octyl group protected

platform, the efficiency drops significantly with 2-15 and the extraction ability becomes almost

zero with 2-16 under the same conditions. Insolubility of the metal complex being formed

during extraction is the most likely reason for the problems related to the extractions with these

ligands. In case of 2-15, although it shows moderate extraction with low concentration of

COSAN and ligand concentration, when COSAN and ligand amounts are increased, it extracts

metals 100 %.

In order to determine the extraction abilities of 2-15 and 2-16 in different solvents,

extractions were performed in 1-octanol solution with COSAN. Neither of the ligands showed

any extraction under these conditions.

These results clearly show that extraction efficiencies of the ligands are strongly dependent

on the type of the triphenoxymethane platform, the concentration of the synergist and the solvent

used during the extractions. Due to the high extraction abilities of 2-13, 2-14 and 2-15, under

specific conditions mentioned for this particular ligand, these ligands are likely to be successful









candidates for the nuclear waste treatment. Therefore extraction experiments with the actinides

must be performed to see their extraction capabilities with these metal cations.

According to the results of Smirnov and his coworkers, DPA ligands show successful

separations between the actinide (III) and lanthanide (III) cations. It is probable that our ligand

systems, taking advantage of reorganization with the same moieties, may be even more

successful for selectivity and distribution ratios.

3.2.2.3 Following the extraction efficiency of 2-13 by NMR spectroscopy

After having seen the high extraction efficiency of 2-13 with high distribution ratios for the

lanthanides, NMR scale extractions were performed with this ligand with various concentrations

of COSAN and the ligand in CD2 12. Lutetium was used as the metal because it is diamagnetic

and therefore enables monitoring of extractions by NMR spectroscopy. First, an NMR spectrum

of lx10-2 M 2-13 solution in CD2 12 WAS taken. The ligand solution was then stirred with 1 M

nitric acid solution for two hours. Since extractions are performed in strongly acidic solutions, it

is possible that protonation or deformation of the ligand may occur. In this case, on the NMR

timescale, protonation of the ligand is not observed. Overlaid spectra for these two particular

cases are depicted in Figure 3-2. Having tested the stability of the ligand in the acid solution, a

COSAN-ligand solution was stirred with the metal-containing nitric acid solution. To determine

the efficiency of the extraction, different concentration ratios were used. When equal

concentrations of COSAN, ligand and metal were used, the extraction did not go to completion

according to the NMR spectrum. In addition to the peaks of C3-Symmetric species formed, free

ligand peaks were also observed. With concentrations of the ligand and of COSAN at one and a

half times that of the metal, the same result with mixture of free ligand and the product was

observed. Another trial was performed with the concentrations of both ligand and CO SAN being

three times that of the metal ion. In addition to the product, the excess ligand peaks were also









observed. The final trial was using equal concentrations of ligand and metal and three fold excess

of COSAN. The NMR spectrum is given in Figure 3-1. It can be clearly seen that metal was

extracted 100 %. Moreover, the new species formed is a C3-Symmetric species. The very top

spectrum, a, shows the aromatic region of the ligand before processing with acid. The middle

spectrum, b, shows the aromatic region of the ligand after stirring in 1 M nitric acid. The last

spectrum, c, shows the aromatic region of NMR spectrum of the species formed after stirring the

lx 10-3 M metal solution with 3x10-3 M COSAN and 1x10-3 M ligand solution in CD2 12.

When these spectra are compared, it is seen that the singlet peak for the central carbon hydrogen

is shifted from a[[roximately 6.40 ppm to 6.70 ppm after the extraction. The doublet peak

originating from the triphenoxymethane platform around 6.80 ppm is shifted to 7.30 ppm. The

second doublet seen around 6.95 ppm remains at the same location. The third aromatic peak for

the triphenoxymethane platform is shifted from 8.02 ppm to 7.20 ppm. Aromatic peaks of the

triphenoxymethane platform are not the only peaks shifted after the extraction; the pyridine

peaks coming from the DPA groups are also shifted. The doublet of doublets around 7.70 ppm

shifted to 8.10 ppm, the triplet peak at 8.00 ppm shifted to 8.55 ppm and the second doublet of

doublet peak shifted from 8.25 to 8.40 ppm for the peaks coming from the of the ligand. The last

singlet on the spectra corresponds to the aromatic NH peak. This peak is originally at 9.60 ppm

and is slightly shifted to approximately 9.70 ppm after the extraction experiment.

The NMR scale extraction experiments clearly showed the extraction of the metal (III) ions

by the formation of the expected C3-Symmetric complex.

3.2.3 Solid State Structures of 2-10, 2-13, and [2-10 M]3+, (M=TmI, Yb)

The crystal structures of 2-10 and its metal complexes with Tm and Yb are given in Figure

3-2 and Figure 3-3, respectively. Structural and preliminary refinement data are presented in

Table 3-1 and selected bond lengths for the compounds are given in Table 3-2. The metals nicely









fit in the nonadentate coordination site of the ligand with two carbonyl oxygens and one nitrogen

atom on each arm of the tripodal ligand coordinating to the metal. The geometry around the

metal for both of the metal complexes is tricapped trigonal prismatic (TTP). The oxygens of the

carbonyl groups at the coordination site are located in the triangular planes and the pyridine

nitrogens that form bonds with the metal cap the faces of the triangular prism. Both complexes

are C3-Symmetric. In each of the structures one M (NO3)52- (M= Tm, Yb) and one NO3~ aef

present as counter ions to neutralize the [ML] 3+ mOiety.

Binding to the metal has little influence on the CO bond distance. The bond lengths of Ln-

O amidee) and Ln-N pyridinee) for different complexes of DPA are reported, and these bond

lengths are standard with certain values." According to the literature, the bond lengths for Tb-O

with the carbonyl groups is between 2.356- 2.415 A+ and for the pyridine nitrogen and the metal

bond, Tb-N, the given bond lengths are between 2.49- 2.54 A+. When the bond lengths of Tm and

Yb with amide oxygen and pyridine nitrogen are compared with those of N, N, N', N'-

tetraalkylpyridine-2, 6-dicarboxamide (ONO)-Ln type complexes reported in the literature, there

is a close match. Some of the bond lengths are slightly shorter than the literature data within thud

limits of acceptable error. When metal-oxygen (M-O) bond lengths of the [2-10Tm]3+ COmplex

are compared with those of the [2-10Yb]3+ COmplex, a slight decrease is observed due to the

smaller size of Yb relative to Tm. A similar trend is observed with the metal-nitrogen (M-N)

bond lengths of the two complexes.

When the metal-oxygen bond lengths at the prism oxygens of the Yb complex are

compared with the reported metal-oxygen bond lengths of [Yb(H20)9 3+, it is observed that the

metal-oxygen bond lengths are slightly longer in Yb complex than those of the nonaaqua

complex. The reported value for the oxygen distances of the [Yb(H20)9 3+ 1S 2.302(2) A+.









Table 3-1. X-ray data for the crystal structures 2-10, 2-13, and the metal complexes of 2-10 with
Tm and Yb.
2-10 [2-10Tm]3+ [2-10Yb]3+ 2-13
crystal system triclinic triclinic triclinic triclinic
space group P-1 P-1 P-1 P-1
a(A) 13.2708 12.3444 12.3925 11.8611
b (A+) 20.2314 20.6250 20.7800 13.7400
c (A) 34.4564 23.7115 23.7387 18.8106
a (deg) 102.395 65.668 65.697 96.6469
B (deg) 95.514 76.628 76.299 90. 1072
Y (deg) 98.011 81.309 81.289 97.8883
Vc (A3) 8871.02 5441.03 5402.77 3015.690
pu(Mo Ka) (mm l) 0.07 1.84 0.98 0.06

The average distance of the oxygens in the Yb complex is 2.34. Therefore there is only

0.03 8 A+ difference between the bond lengths of the oxygens. In the case of a previously studied

C3-Symmetric diglycolamide (DGA) complex this difference is 0.011 A+.76 In COmparing the

metal-nitrogen bond distances with the equatorial oxygens of the nonaaqua complex, the metal-

nitrogen bond distance is 0.068 A+ shorter than that of the nonaaqua complex, which is reported

to be 2.532(3) A+. The DGA complex however, is reported to have metal-oxygen bond distances

0.103 A+ shorter than the nonaaqua complex.

The twist angles between the two triangular planes were also determined for both of the

complexes. For the Yb complex it is 11.40 and for the Tm complex it is 9.60. The trigonal prism

is twisted by 15.20 in the Yb3+ DGA and this distortion away from the idealized TTP geometry

increases with the size of the metal ion.76 Unfortunately, with 2-13 it was not possible to obtain

single crystals with any Ln(III) due to solubility problems.

When the two C3 Symmetric complexes are compared although DGA ligand is more tightly

bonded to the metal cation, the twist angle, which are the main criteria for the deviation from

ideal trigonal prismatic geometry, for the DPA complex is lower. Therefore, nonadentate DPA

provides a coordination site that is closer to the ideal for (TTP).









The extraction behavior of the nonadentate DGA ligand appears to be related to the

distortion angle in such a way that extraction efficiency dropped with the increase of the twist

angle.76 Unfortunately, nonadentate DPA ligand does not show that behavior. When extraction

results are considered, 2-10 showed moderate extraction towards lanthanides even in the

presence of the synergistic COSAN. In the DGA system, although the solid state structure

showed higher distortion relative to DPA system, the DGA ligand showed high extraction

effciency.

To predict of extraction behavior of the ligands, another factor can be considered regarding

the solid state structures of the ligands. It can be argued that tighter bonding of DGA system to

the metal cation relative to DPA system makes the extraction effciency higher for DGA system

when compared to 2-10. However this discussion would not be relevant either because with the

DGA system, it was determined in solid structure that Ce(III) complex has shorter metal-oxygen

bond length than Yb (III) complex. The problem is that the extraction effciency for Ce(III) is

less relative to Yb(III) complex which has longer metal oxygen bond lengths and smaller twist

angle.76

It is difficult to correlate the extraction behavior of DPA directly to its solid state structure.

Lack of crystal structure of the complexes with other derivatives of the ligand makes it even

harder to make a conclusion. The extraction behavior of the ligand might be more related to

solubility issues which will be discussed in the next section.

A solid state structure of the lower side functionalized triphenoxymethane platform with

the methyl protected derivative, with ethyl substituents, 2-13, was obtained.(Figure 3-4). The

structure of this ligand is given in Figure 3-4. The X-ray data and the bond lengths of the

carbonyl groups are depicted in Table 3-1 and Table 3-2, respectively. In X-ray data, three arms









with the pyridine-diamide moieties attached from the para positions of the phenyl groups of the

triphenoxymethane platform are clearly observed. The DPA moieties are attached through their

carbonyl groups to the NH groups of the triphenoxymethane platform. In the structure, the

methyl groups of the methoxy groups are pointing toward the outer part of the platform. In this

way they are as far away from each other as possible.

Unfortunately, in spite of efforts to crystallize metal complexes of this ligand and the other

derivatives of the lower side functionalized ligands, crystals suitable for X-ray analysis were not

obtained.

3.3 The Factors Affecting the Extraction Performance of Nonadentate Pyridine-2, 6-
dicarboxamide System

Prediction of the extraction behavior of any ligand system is not easy because there are

several factors at play. The structure of the extracted complex is not actually known. Moreover,

the extractions are performed in organic diluent- aqueous acidic systems, which increase the

factors contributing to the extraction process. There is competition between the organic solvent

and the water in terms of solvation. There is also competition between the acid proton and the

tripositively charged metal cation in terms of acting as a Lewis acid particularly for systems

bearing basic groups such as amine or pyridines.

All these factors affect the extraction efficiency of a ligand. Moreover, since the f-block

elements can form complexes with a wide range of coordination numbers, the probability of

determining the nature of the extracted species is low. Above all, the solubility of the ligand in

the organic phase and of the resultant complex in both the aqueous and the organic phase are

important to consider.









Table 3-2. Selected bond lengths (A+) for the 2-10, 2-13, and metal complexes of 2-10 with Tm
and Yb.
2-10 [20-10Tm]3 [2-10Yb]3 [2-13]
C(1) O(1) 1.241 1.246 1.247 1.225
C(2) O(2) 1.244 1.247 1.267 1.235
C(3) O(3) 1.213 1.254 1.256 1.226
C(4) O(4) 1.245 1.234 1.243 1.235
C(5) O(5) 1.264 1.224 1.218 1.228
C(6) O(6) 1.241 1.258 1.222 1.238
M O(1) 2.355 2.324
M O(2) 2.350 2.318
M N(1) 2.490 2.475
M O(3) 2.328 2.326
M O(4) 2.324 2.350
M N(2) 2.471 2.468
M O(5) 2.349 2.358
M O(6) 2.366 2.364
M N(3) 2.464 2.458


The extraction efficiencies of the ligands are strongly dependent on the solvent, the type of

triphenoxymethane platform, the liphophilic character of the ligand system and the concentration

of the synergist used. Among these, the effect of CO SAN is the most important one because

none of the ligands show any extraction towards lanthanide ions without CO SAN in any solvent.

CO SAN is acting as a large liphophilic counter ion which renders the resultant complexes

soluble in the organic phase such that transfer of the complex to the organic phase is facile.

The type of triphenoxymethane platform used is also important. The liphophilicities of the

ligands are closely related to the type of the tripohenoxymethane platform, which also greatly

affects the solubility. All these considerations make the solubility a maj or factor in the

determination of the extraction behaviors of the ligand systems. Starting with the

triphenoxymethne platforms used in this study, the most polar is the methyl protected lower side

functionalized triphenoxymethane platform. The second most polar is the octyl protected

triphenoxymethane platform, and the least polar is the upper side functionalized









triphenoxymethane platform. The main obj ective of the extraction experiments in terms of

solubility is to provide the right solubility environment for the complex formed. The most

effcient ligand system of those studied is the methyl protected lower side functionalized

triphenoxymethane platform with methyl protection. The ligands with this platform, both with

ethyl and isopropyl derivatives, show high extraction performance with almost the same

effciency, the ethyl derivative being slightly more efficient than the isopropyl derivative. The

extraction efficiency of the octyl derivative drops when compared to methyl protected

derivatives under the same extraction conditions. The efficiency of the octyl protected ligand

with the ethyl substituent is approximately 20%, while the methyl derivative extracts 100 %. The

extraction efficiency of the octyl protected triphenoxymethane platform with isopropyl groups is

almost zero. When the concentration of CO SAN is tripled, the ethyl derivative of the octyl

protected ligand works as efficiently as the methyl protected ligands. From this observation it is

obvious that the problem is not the matter of having bulkier ligand that prevents the metal

coordination, but rather the solubility. The isopropyl derivative of the octyl protected

triphenoxymethane platform forms a complex which is too no polar in 1, 2-dichloroethane or in

CH2 12. The same problem occurs with the upper side functionalized triphenoxymethane

derivatives. Even in the presence of CO SAN none of these ligands show any extraction towards

lanthanides. Again, complex formed is too nonpolar to be extracted into the organic phase.

Another problem of solubility related extraction inefficiencies is due to the solvent itself.

In the extractions with 1-octanol, none of the ligands showed any extraction for the lanthanides,

even in the presence of CO SAN. The solvent is very nonpolar, and none of the ligands are able

to provide the right solubility conditions to work effciently.









Considering all the factors discussed above, solubility is most likely the reason for the

different extraction behaviors of the ligand systems with nonadentate DPA ligand system.

Although there are other factors, including different species being formed during the extraction

process, and all the important points mentioned in the beginning of this section, solubility is most

likely the one, depending on the experimental data and on the solid state structures of the two

complexes discussed earlier.

There is one important thing that needs to be pointed out. The DGA system studied

previously shows the opposite trend in terms of extractions depending on the type of the

triphenoxymethane platform when compared to DPA system. While the pyridine-2, 6-

dicarboxamide system shows good extractability with the lower side functionalized

tiphenoxymethane system and shows poor extraction with upper side functionalized

triphenoxymethane platform, the DGA system shows no extraction with the lower side

functionalized triphenoxymethane platform and shows high extraction performance with upper

side functionalized triphenoxymethane platform. This situation cannot be explained in terms of

difficulties with the coordination site binding to the metal cation. Both ligands are capable of

coordinating to the metal. The main difference between the two ligands is that DGA is more

polar than DPA. Since the extracted complexes are soluble under only certain conditions

depending on the counterions, the triphenoxymethane platform used and the solvent used during

extractions, the differences of the polarities of these ligands may be playing an important role in

terms of extraction behaviors. As discussed previously, the ideal ligand for high extraction

efficiency with the DPA moiety is the methyl protected lower side functionalized

triphenoxymethane platform. The other two platforms make the ligand too non-polar, and they

tend to lose their extraction efficiencies. However, when more polar digylcolamide is attached to









the relatively less-polar upper side functionalized triphenoxymethane platform, the ideal

condition is achieved in terms of solubility. However, with the more polar lower side

triphenoxymethane platform the ligand is too polar and looses its extraction ability because the

metal complex is no longer soluble. Regarding the DPA system, introducing this relatively more

less-polar moiety with respect to DGA to the least polar triphenoxymethane platform, the ligand

becomes too non-polar to extract the species forming during extraction. This discussion stems

from the fact that lower side functionalized DPA ligands are soluble in solvents with a narrow

range of polarity. As an example, methanol is too polar to be soluble in for 2-13 and diethyl ether

is too nonpolar to be soluble in for the same ligand. If the ligand is behaving this way, the

complex formed will act parallel to it, and will have narrow range of solubility within the

common solvents.

3.3 Conclusion

The ligand systems designed, bearing both pyridine and diamide moieties providing nine

coordination sites with two different types of triphenoxymethane platforms were synthesized.

The extraction properties of these ligands indicated that without a synergist they are not efficient.

The upper side functionalized triphenoxymethane platform derivatives of the ligands were not

efficient, even in the presence of the synergist CO SAN. However, when the synergist CO SAN is

used with the lower side functionalized triphenoxymethane platform, the lanthanide cations are

extracted up to 100 %. Due to solubility differences, octyl group protected triphenoxymethane

derivatives are less efficient than the methyl protected triphenoxymethane platform derivatives.

The extraction experiment for 2-13 was repeated on NMR scale and 100 % extraction can be

clearly seen from the data when using a ratio of 3: 1: 1 of COSAN: ligand: Ln.

To elucidate the efficiencies of these ligands with actinide (III) cations, experiments should

be performed with these cations.










Crystal structures of 2-10 and its metal complexes with Tm and Yb were analyzed. The

coordination site has tricapped trigonal prismatic geometry. The metal-oxygen and metal-

nitrogen bond lengths are in agreement with the literature data. The twist angles of the

complexes are approximately 90 and 110 which is a negligible deviation from ideal TTP

geometry.

3.4 General Procedure for the Preparation of [2-10Ln] [Ln(NO3)s] [NO3] (Ln= Tm, Yb)

A solution of 0.8 equiv. of Ln(NO3).xH20 in CH3CN was added to a solution of 1.0 equiv.

of 2-10 in CH2 12 and the mixture was stirred overnight. The solvent was removed under

vacuum and the solid residue was washed with ether and filtered. Slow diffusion of pentane into

a CH2 12/CH30H solution of the complexes afforded crystals suitable for X-Ray analysis.

[2-10Ln] [Yb(NO3)5] [NO3]: Calculated for CssH121N15O27 2:: C 48.95, N 9.48, H, 5.89;

Found C 49.34, N 9.19, H 6.09.

3.5 X-ray Crystallography

The crystal structure analyses of all molecules were performed by Dr. Michael J. Scott.

Unit cell dimensions and intensity data were collected on a Siemens CCD SMART

diffractometer at 173 K. The data collections were nominal over a hemisphere of reciprocal

space, having a combination of three sets of exposures. Each set with a different qb angle covered

0.30 in co. The distance of the crystal to the detector was 5.0 cm. The correction of the data sets

for absorption was achieved by SADABS by measurement of crystal faces. Broker SHELXTL

software package for the PC was used for solving the structures by applying either direct

methods or Patterson functions in SHELXS. The space group determinations of the compounds

were done from an examination of the systematic absences in the data.

























99 9 9 1I p 9 r


e' n u a oro I p


ah


I IIII I I II I
95 BJ ILS IUI 75 Ta eA


s~-JLC~--_~_JEd~LU


Figure 3-1 N\MR scale extraction data with 2-13. A) lx10-2 M ligand in CD2 12, B) lx10-2 M
ligand after being stirred in 1 M nitric acid, C) C3-Symmetric extracted complex
formed after the extraction with 1x10-3 M Lu, 3x10-3 M CO SAN and 1x1 0-3 M of 2-
13.


,~d I,


1_

















Figure 3-2 Crystal structure of 2-10.


ic,


ke
;C^i' A
Clr2^2cc
1'7'
X"i?`` Ls
~"
c7" r?
Figure 3-3 Crystal structures of [2-10 M]3+, M= Tm, Yb.


































Figure 3-4 Crystal structure of 2-13.









CHAPTER 4
INTTRODUCTION

4.1 Porphyrins

Porphyrin is a heterocyclic macrocycle that consists of four pyrrole units linked by four

methine bridges from their a-carbons, as shown in Figure 4-1. The bridging methane carbons are

called meso carbon atoms. The carbon atoms at the outer part of the pyrrole rings are called the

P-carbon atoms.

Free base porphyrins and their metal analogues play an important role in many biological

processes, including absorption of sunlight and electron transfer for the initial step of

photosynthesis91 and oxygen transport and storage taking place in hemoglobin.92 Porphyrins and

their derivatives are also used as catalysts in industrial processes, and as photosensitizes in

photodynamic therapy.93 They are important as organic semiconductors and nonlinear optical

materials with their extended xn-electron systems.94 They also form an important class of aromatic

dyes.95

Porphyrins have interesting spectroscopic properties which are affected by the type of the

central metal atom, types of the substituents and their locations,97 and aromatic fusion of

molecules to the porphyrin ring system. As a result the interest in the experimental and

theoretical studies on the UV-Vis spectra of porphyrins has been increasing.

4.2 Gouterman's Four Orbital Model for the Spectroscopic Properties of Porphyrins

The experimental near-UV-Vis absorption spectra of porphyrins exhibit a weak absorption

in the visible region at approximately 550 nm which is referred to as Q band.98 In addition; there

is a very strong absorption band at around 400 nm in the near-UV region. This band is called the

Soret band or the B band.98 Both the Q and B bands result from xn-x* transitionS96 and are

explained by Gouterman's theory with four orbital model.99 According to four orbital model,









the Soret bands and the Q bands are taking place due to the transitions between the two top filled

orbitals and the two lowest unoccupied orbitals of the porphyrins.99

As it is seen in Figure 4-2a, for the perfect D4h symmetry the two top filled orbitals,

HOMO-1 and HOMO orbitals, are accidentally almost degenerate and have al, and atu

symmetries, respectively. These two orbitals have different electron participation and nodal

structures.100 The meso-carbons of atu Orbital have high electron density but the electron

participation on the P-carbons is very low. The situation is the opposite for the al, orbital. The

participation on the P-carbon atoms is very high and there is none on the meso carbon atoms.101

The two lowest unoccupied orbitals (LUMO) are degenerate and have e, symmetry. The excited

state configurations of these orbitals, as shown in Figure 4-2b, are al/leg (HOMO-1 leg ) and

azul 1l (HOMO eg ). The symmetries of these transitions are Eu in D4h point group and these

transitions have two equivalent dipole transitions in the x and y directions.99 These

configurations are nearly degenerate and they generate a strong configuration interaction (CI)

which results in a high-energy state and a low energy-state.102 The high-energy state corresponds

to the B-band and the low energy state corresponds to the Q band.102 Due to near degeneracy of

these configurations, their contributions to Q and B bands are not equal.101 The lower energy

configuration, azul 1l (HOMO1 eg ), has more contribution to the Q band and the higher energy

configuration al/leg (HOMO-11 eg ) has more configuration to the B bandlot which is depicted

in Figure 4-2c.

Generally, Qx, Qy, Bx and B, are used as labels for the individual components of the

transition pairs. Qxo, 0,, Bxo, and Bo are the labels for the pure electronic transitions. Qx Qyl,

Bx and B,1 are used for the vibronic overtones of the electronic transitions.99 In case of free

base porphyrin, x and y axes are not equivalent and as a result Qx and Qy bands are split.99









Referring the pure electronic transitions of Q and B states of any porphyrin to QO and Bo

states;99


= [(,L, + (,L, ]/(4-1)

B,
= [(zL,)(HL) ]/(4-2)

In equations (4-1) and (4-2), (HyL2) defines singlet states for the transition H; ~L2, etc.

These states take place when H1, H2 and L1, L2 are degenerate.99 Among the states considered,

QO gives the forbidden visible band, and Bo gives the allowed UV bands. Assuming the states of

different polarization does not mix; it is proven by perturbation theory that for the Q states of any

porphyrin, for each of the polarization, the visible band becomes allowed with the break down of

the equality of the transition energies.99

When the free base formation is considered, the energies of the orbitals change. If the

hydrogens are attached to the second and forth pyrrole nitrogens (Figure 4-1), then L2 will be

lowered with respect to L1.99 It is harder to predict the situation for H1 and H12. As it is given in

Figure 4-3, if H1 is lower in energy, then the energy of x polarized transitions will be close and

the energy of the y polarized transitions will be different. As a result, Q, will be strong and Qx

will be weak. In case of having H1 having higher energy and H12 having lower energy, the

opposite trend will be observed.99

The energetic ordering, the spacing and the molecular orbital (MO) amplitudes of the

orbitals of any porphyrin change depending on the substituentS.101, 103 Electron withdrawing and

electron donating groups determine the stabilizations of the orbitals.lor While placing electron-

withdrawing groups at the meso carbons or inserting a metal ion to the pyrrole nitrogens

stabilizes atu (H12) orbital, placing electron-withdrawing groups on the P-pyrrole carbons









stabilizes alu (H1) orbital.100 Thus prediction of the Q and the B bands depends totally on the

stabilizations or destabilizations of the molecular orbitals with respect to the substituents.

The transition dipoles of the individual transitions are combined by configuration mixing

in such a way that B band has a strong intensity and Q band has a weak intensity.10

Most theoretical calculations are in good agreement with this model, although some studies

comment on the necessity of accounting for more transitions involving lower occupied and

higher unoccupied orbitals in addition to Gouterman model orbitalS.104

4.3 Theory and Computational Chemistry

4.3.1 General aspects of Quantum Chemistry

It is not possible to interpret the spectroscopy, reactivity and the physical properties of a

molecule without understanding the electron distribution in that molecule."o Since classical

mechanics can deal with only the macroscopic particles, for microscopic particles quantum

mechanics (wave mechanics) was developed.106

According to quantum mechanical approach to a system of N particles, all the properties

of the system is in a wave function, uy. This is a function of time and the coordinates of the N

particles."o The wave functions are the eigen functions of the Hamiltonian operator and as a

result the energies are the eigen values of the Hamiltonian operator.ios The wave function is

required to be continuous (including its partial derivatives), normalizable, and finite.106 Also the

probability density represented by a particular wave function should be single-valued.106 In this

way the eigen values of the operator will be meaningful for the properties of the chemical

sy stem.

The wave function is time-dependent when time is included in the wave function. In

order to see the future state of system from the knowledge of the present state, there should be an

equation that shows how the wave function changes with time.106 This concept was pointed out









by Austrian physicist, Schriidinger. Since then, the equation is known as Schriidinger's equation.

The time-dependent Schriidinger equation is given in Equation 4-3.107


87 A2 1 1 1 l 43
dt 2 nt z

In thi s equation, A = 5 ~ where h is the Planck' s constant, i = 0,j m is the mass of the

interacting particles, and V is the potential energy of the system. The equation has the first

derivative of the wave function with respect to time and in this way future state of the system can

be calculated if the wave function at time to is known.106

The system is in stationary state when time is not included in the wave function

explicitly. Then the wave function is said to be time-independent wave function.los Time-

independent Schriidinger equation can be written by using the Hamiltonian given in equation 4-4

assuming Born-Oppenheimer approximation.106 In this equation electrons and nuclei are

assumed to be point masses and spin-orbit coupling and other relativistic effects have been

neglected.

H = 1 & ZBL Z~ Ze (4-4)

Here a and p present nuclei and i and j present electrons. The first term in the equation is

the kinetic energy operator for the nuclei, the second term is the kinetic energy operator for the

electrons, the third term refers to the repulsions between the nuclei, rap is the difference between

nuclei a and p with atomic numbers Z, and Zp.106 The forth term refers to the attractions between

the electrons and the nuclei in which ri, is the distance between electron i and nucleus a. The last

term is the repulsion between the electrons and rij is the difference between electron i and

electron j.10

Time independent Schriidinger equation is as follows:









H7W(r,,........,r,,)> = E7y(r',,......,r,,)> (4-5)
In this equation r7is the position of the ith electron and N is the total number of electrons

present in the system. E represents the total electronic energy of the system.106 The main purpose

of solving Schriidinger equation is to find the coordinates of atoms of the molecule that gives the

minimum energy value, Eo. However, it is very hard to solve the entire equation. The reason for

the Schriidinger equation to be so complicated is that it consists of 3N electron Cartesian

coordinates, N electron spin coordinates and 3N nuclear cartesian coordinateS.106 In Order to

simplify the calculation of the Schriidinger equation, variation method is applied to the

Schriidinger equation. In this way an approximation is applied to the equation for the ground

state energy of the system.106 The main advantage of variation method is that it helps to calculate

an upper bound for the ground state energy.106 The variational principle is defined by Equation 4-




> Eo (4-6)

In this equation, uy is the trial function, ad Eo is the ground state energy. The lowest value

of the integral gives the closest value of the energy the ground state energy.

Computation of accurate self-consistent-field (SCF) wave functions is an important

development in computational chemistry.106 The wave function is written in terms of

antisymmetrized product of spin-orbitals. Each spin orbital is a product of a spatial orbital cp and

a spin function; either a or p.106 These spatial orbitals minimize the variational integral. They are

calculated by solving the Hartree-Fock equationS.106 given in equation 4-7.


H*i(1)uP,(1)= ef,(1) (4-7)
In this equation Ei is the orbital energy. The effective Hartree-Fock Hamiltonian operator

is as shown in equation 4-8.










H (1) = V, C + 2 j, (1) K, (1 (4-8)

The first term is the kinetic energy term for one electron and the second term is the

potential-energy operator taking into account the attraction between one electron and the

nuclei.106 Here J, is the Coulomb operator and K, is the exchange operatorl06 which are

depicted in equation 4-9 and 4-10, respectively.


J, (1)y?, (1) = Gn, (1)5 to (2) 2 1 dv, (4-9)

K,~ (1p 1 =9 1 V, (4-10)

The Coulomb operator defines the potential energy of interaction between one electron

and the second electron with electronic density 9, (2) The factor 2 comes from the fact that

there are two electrons in each spatial orbital.106 The exchange operator does not have physical

interpretation but comes from the fact that the wave function needs to be antisymmetric with

respect to electron exchange.106

4.3.2 Basis Sets

Hartree-Fock calculation is the calculation for which SCF uses antisymmetrized spin

orbitals. Hartree-Fock orbitals can be written linear combinations of a complete set of known

functions, basis functionS.106 The orbitals that are being used during calculations should be

defining the shielding effects if the other electrons in the system, as a result they should follow

certain rules for the effective atomic number.10s One of the most commonly used set of orbitals

are Slater type orbitals (STO). In equation 4-11 the equation of STOs in polar coordinates are

given.

uyn, 1, m(r,6, cp)= NY1,m(69p)r"- e-gr (4-11)









In this equation n is the principle quantum number, I is the angular momentum quantum

number and m is the magnetic quantum number; Yi,m is a spherical harmonic.10 N is the

normalization constant in the equation and the parameter 5is defines as orbital exponent.106

In order to make calculations simpler, another type of orbitals were proposed called

Gaussian type orbitals (GTO). In equation 4-12, the equation of GTO is given in polar

coordinateS.106


un,~ 1,m (r,6, cp)= NY1,m (69p)r' e (4-12)
As in Stops, N is the normalization factor, Yi,m is the spherical harmonic and 5 is the

orbital exponent. Unlike STOs with an exponential factor of exp(-5r), GTOs have an exponential

factor of exp(-5r2 .106 For smaller numbers of r, the Gaussian function defines the atomic orbital

in a poor way because Gaussian functions do not have cusp when r is small. In order to

overcome this deficiency, linear combinations of several Gaussians are used to define an atomic

orbital as a result of which the number of integrals used in SCF calculation with GTOs is more

than that of STOs.106 In Spite of this fact, calculations with GTOs take less time than STOs

because the product of two Gaussian functions at two certain points gives a single Gaussian at

the third point.106

When the basis functions are considered, each molecular orbital is defined as a linear

combination of one-electron orbitals centered on each atom.106 SCF calculations can be carried

out by two different methods: Methods that use minimal basis set or methods that use extended

basis set of atomic orbitalS.106 A minimal basis set contains only inner shell and valence shell

atomic orbitals. An extended basis set uses inner shell and valence shell atomic orbitals in

addition to higher shell atomic orbitalS.106 Minimal basis set calculations are easy but extended

basis set calculations are more accurate.106









4.3.3 Density Functional Theory

4.3.3.1 Hohenberg-Kohn theorems

When the Schroidinger equation is considered that is discussed previously, for an N

electron system, 3N coordinates are taken into account during calculations and due to electron-

electron interactions the equation cannot be reduced into simpler form.109

One-electron density matrix, given in equation 4-13, or the two electron density matrix,

as in equation 4-14, describe most experimental observableS.109



'1 N(N 1)2 7 l~7i ~i ~i.. ~ ~~ry (-4
p (zj~r,,r ',r '= y *(7jF,,4,....,4 ) ( 'r', ... ,) .d 4- )
The electron density in position space is defined in equation 4-15.

p(F = r(,F (4-15)
According to Hohenberg and Kohn, the electron density p(F') of the ground state defines

the external potential Va( ) so the electron density in three-dimensional space is enough to

write the full Hamiltonian operator which will lead to the solution of the Schroidinger

equation.109 Therefore any ground state property can be determined and any ground state

property is considered to be a functional of p(F').109 There is an important thing to be indicated

at this point. This theorem is a theorem that proves the existence of the functionals but the

theorem does not explain how to obtain these functionalS.109

The total electronic energy (E) is a ground state property and it is defined as a functional

of electron density with respect to Hohenberg-Kohn theorem.109 This relation is given in

equation 4-16.

E=E[p] (4-16)
Also total number of electrons (N) are considered to a functional of p.109 This relation is

given in equation 4-17.









N= ~p(F~d (4-17)
Another relation that was proved by Hohenberg and Kohn is that any trial density

obeying equation 4-17 also obeys the following equation, 4-18.109

EQ]>2 E o] (4-18)
The relation given in equation 4-18 indicated that Hohenberg-Kohn theorems consider

the calculation of the total electronic energy whenever variational principle is applied.109

4.3.3.2 Kohn-Sham equations

The total kinetic energy of the system is considered to be a ground state property and it is

a kinetic energy functional of electron density,109 as seen in equation 4-19.

T=T[p] (4-19)
It is also possible to write the external potential and the classical Coulomb energy (Ve) as

a function of density.109 They are given in equations 4-20 and 4-21, respectively.

Ip(r') Vx, (F)d (4-20)
e p( ) p( ,) g & V( F)p ( F) c (4-21)


The total energy y functional, E[p], can be written as follows;


E~p= ~p+ (F)Ve,()+Vlf) Idr+txc[p] (4-22)

The term with 5[p] is called as the exchange-correlation energy functional and it contains

all the non-classical interactionS.109

When variational principle is applied including the relation given in 4-20, via langrange

multiplier, following equation is achieved;

3 E- pF~F -N 0-> + Vx () >+y, Vc)+ 3 = pu (4-23)

This equation was compared with the one obtained that had N interacting particles

moving in another external potential Vett, the total density of both systems were determined to be









equal.109 As a result, equation 4-24 was achieved in which T;[p] represents the kinetic energy of

the non interacting particles.


+ V, (r) = pu (4-24)
The Schroidinger equation for N particles can be solved easily because it can be

separated into N equations in the following way;109


V ( ) 7 ( ) =Ez7 7 (4-25)
And the total density of these N particles is given by equation 4-26.


p(F) f V (7)(4-26)
When equations 4-23 and 4-24 are compared following equations are derived;109


V, (r) = Vex, (r) + Vc (r) + + --- -Vx ()+V()+
6p 6p 6p I p (4-27)

According to this equation;

6E~
Vc ('") = and E, = 5, + T -T (4-28)
The total energy of the N individual electrons is basically sum of their indivi dual energies

but it is not the same for the real system.109 The total energy of the real system is given in

equation 4-29.


E4p]= Vm2 r + 1, +r p() x(F+ c F) +,[p] (4-29)
This equation can also be written as;


E4p]= e, p(I=) Vc[ (7 y(7 x [p] (4-30)
Vxc and Exc are electron density ( p(F)) functionals and their relation with electron

density is seen in Equation 4-28. Vxc is defined as a function of three-dimensional position









coordinate but it is also dependent on the behavior of electron density, (p(F)).109 The precise

form of Vxc is not known.109

During calculations of a system homogenous electron gas is considered. This approach

builds a simple system with accurate quantum mechanical calculationS.109 However, for some

systems in which electron distribution is not homogenous, local-density approximation (LDA) is

used.109 In this approximation Vxc, which is a function of the position coordinate r', is

calculated at point F~' to find out what it would be at that point if it were homogeneous electron

gas at that point.109 This approximation neglects the effects dues to variations in electron density,

p(F). On the other hand, this approach s parameter-free.109 Since during calculations for the

properties of the system integrals over all the space are taken into account, some errors are

averaged out.109

In some cases LDA calculations are not efficient for accurate results so non-local

functionals are improved which are the functionals of [Vpl and V~p as well as p.109

In order to achieve better results, there have been attempts to combine Hartree-Fock and

DFT methodologies to make hybrid methods.109 among these attempts; the most successful one

is with Becke's three parameter exchange functional with Lee, Yang Parr (LYP) correlation

effects. There have been accurate results with these functionals but calculations become more

extended since the number of parameters increase with these functionalS.109 The advantage of

these approximate functionals is that they are parameter-free and they are general for all systems,

atom types and structureS.109

4.3.4 Electronic Spectroscopy

When thee electric field component of radiation interacts with a molecular system, the

radiation is absorbed by the molecule."o The absorption takes place when the radiation matches









the energy difference between the quantized energy levels of different states of the molecule."o

This change in the electronic state of the molecule takes place when an electron in the bonding or

nonbonding molecular orbital of the molecule in its ground state is excited into an empty

molecular orbital at higher energy.'os The Morse potential in Figure 4-4 shows the transitions for

absorption and emission between the electronic ground and excited states.'os

There are different methods to calculate the electronic transitions of the molecules.

Configuration interaction is a common method among all these methods. Wave functions

defining only single configuration are not true wave functions of the Hamiltonian operator since

they do not contain electron correlation.110 The correlation is the contribution of the higher states

to the state of interest with comparable symmetry.110 By the mixing of different excited state

configurations, the wave function converges into the true wave function.110

Another method for the calculation of excited states is the time dependent density

functional theory (TDDFT). According to the central theorem of TDDFT (Runge-Gross

theorem), there is a one-to-one correspondence between time-dependent potential, V,, (F, t) and

the electronic density, p(F', t) ."1 As a result, if the density of a system is known, the external

potential can be calculated. In this way Schroidinger equation can be solved."l It is important to

know the initial state of the system.

In order to construct a time dependent Kohn-Sham scheme, noninteracting electrons under

external local potential VKS .11 This potential is chosen in a way that the density of the

noninteracting orbitals and the density of Kohn-Sham electrons are the same."' The Kohn-Sham

electrons follow the time-dependent Schroidinger equation given in equation 4-31.


7-pr~t= HK(F~~p,(~t)(4-31)
Kohn-Sham Hamiltonian is given as follows;









H(F,~ t) =V 2- + VKS [p](F~, t) (4-32)
To be able to calculate the density of the interacting system from the calculated Kohn-

Sham orbitals,ll equation 4-33 is used.


p(F, ) = ep(, t)(4-33)
The time dependent Kohn-Sham potential is depicted in equation 4-34.

VKS [p](F, t) = Vex(F, t) +~~ V oartre p(f, ) + V,[p](F,~ t) (4-34)
The first term in equation 4-34 is the external potential, and the second term is the

electrostatic repulsion term between the electrons which is given in equation 4-35.11


V;artree (,F, t) = d3 Pr (4-35)
Ir r
The last term in equation 4-34 is the XC potential that contains nontrivial many-body

effects. "l It has an unknown functional dependent on the density both in space and in time."l It

is important to make a careful approximation for XC potential because the quality of the results

are related to the approximation made for this potential. This is the only maj or approximation

in TDDFT like that of in ground-state DFT. "1
















P-carbon atom


meso-carbon atom


Figure 4-1 Structure of porphyrin.


L1 L2_ LUM)O





HOMO-1 H2HOMO
(alu) H1 (a2u)


Wavelength I nm


alu H1 au H2


A B C

Figure 4-2 Gouterman's four orbital model for a D4h porphyrin. A) Schematic representations of
electron densities for the two HOMO and two LUMO orbitals. B) Mixing of four
allowed transitions within the four orbitals via configuration interaction (CI). C) The
absorption spectrum of porphyrin and the contributions of higher energy
configuration, al/l eg to the B band and the lower energy configuration to the Q
band.


81.11~%~1

























H1 H2
Figure 4-3 Possible transitions among the four orbitals of the porphyrins with the change of
ordering of the orbitals.
















I xie tt


Vibrational Rotational
Energy Level Energy Level
Nuclear Coordinates


Figure 4-4 The transitions for absorption and emission between the ground and excited states.'os









CHAPTER 5
COMPUTATIONAL CALCULATIONS FOR CIS-AZULENEONE AND TRANS-
AZULENEONE

5.1 Computational Approach to Porphyrins and Porphyrin Derivatives

The interesting spectroscopic properties of porphyrins have attracted computational

chemists to work on these molecules. Computational studies with different calculation methods,

semiempiricall111, 112, Hartree-Fock (HF)113, 114, pOst-Hartree-Fock 15, 116 (methods that are

developed to improve HF), and Density Functional Theory (DFT),117 Il have been applied to

different porphyrin derivatives and the efficiency of these methods have been compared with

respect to each other.96 In these studies post Hartree-Fock methods turned out to be very costly.

DFT method has become the most common method for porphyrin type molecules91, 92' 101, 118-124

because, unlike ab initio and/or semi empirical HF methods, it takes into account electron

correlationsl25 that are necessary for porphyrin type molecules. Therefore it is more successful

and more reliable for the geometry optimizations and energy differences between the electronic

states of these molecules in terms of being consistent with the experimental results. Studies also

revealed that using higher level of theory rather than using larger basis set gave much better

results.126 For the excited state calculations the most reliable method was determined to be time

dependent density functional theory (TDDFT) over single excitation configuration interaction

(CIS or CI-Singles) calculations.93, 127, 128 It is being used for porphyrin systems95, 129 because

only TDDFT is able to provide extensive configuration mixings that characterize the excited

states of porphyrins and their derivativeS.102

Although many studies have been done with the porphyrin derivatives, molecular orbital

studies for the expanded porphyrin systems, porphyrins containing fused aromatic units, are very

rare. These porphyrin systems show interesting spectroscopic characteristics because they shift









the absorptions to lower energies or they lower the symmetry of the molecule so that degenerate

transitions are split.130

Keeping these facts in mind we were interested in two different isomers of exceedingly

large free base porphyrins, cis-Azuleneone, 5-la, and trans-Azuleneone,~trtrtr~r~r~ 5-2a, reported

previously, bearing bis(naphthoazuleneone) ring systems,131 as depicted in Figure 5-1. According

to electronic absorption spectra of these molecules, the Q bands of both of the isomers were red

shifted to near-IR region.131 The trains isomer was more red shifted than its cis analogue.131

Electrochemical data for cis-Azuleneone was consistent with the spectroscopic data for the

lowest energy absorption.

In order to understand the experimental behaviors of these two expanded porphyrin

systems, we performed DFT calculations on the simplified derivatives of 5-la and 5-2a. These

simplified derivatives, 5-1b and 5-2b, were created by replacing the mesityl and tert-butyl

groups on the molecules by hydrogens to make the computational calculations easier. The

structures of 5-la, 5-2a, and optimized structures of their simplified derivatives 5-1b and 5-2b

are given in Figure 5-1. TDDFT was applied for the excited state calculations. Experimental and

computational data were compared and the results were predicted depending on the calculated

molecular orbitals.

5.2 Computational Methods

The structures of 5-1b and 5-2b were created by Hyperchem 7133 prOgram and were

optimized by density functional theory by using Becke's three parameter hybrid functionall34' 135

combined with Lee-Yang-Parrl36 COrrelation functional, B3LYP, with 6-31G basis set by using

the Gaussian 98137 prOgram. Symmetry constraints were applied to the optimized structures of

the molecules in order to achieve the desired point groups. The structures were verified to be

minima by frequency calculations with the same basis set. Single point calculations for Kohn-









Sham orbitals were carried out with 6-31G* basis set. TDDFT calculations for the excited states

were performed with the same basis set used for the single point calculations. All the calculations

were performed by high performance computers at QTP at University of Florida. During the

calculations Xena II system was used which is considered as high performance cluster to solve

computational problems under Xena Cluster Proj ect at Quantum Theory Proj ect at University of

Florida. This system has 192 nodes. Each of these nodes has a 135 IVHz POWER2SC CPU, 1

GB of RAM and 9 GB of disk space.138 The nodes are connected by a redundant path SP switch

with a 150 1VB/sec rate. The global storage of the system is 420 GB. It has 192 2.2 Gb disks on

16 SSA adapters. These adapters are connected to each node as a general parallel file system

(GPFS) through the SP switch.138














H Ar H


MH H


0 O


R H

H H


N N-


\H


~N N

Ar H


5-la


5-1b (Cs)


SAr H

N N :~---:


NN


H 9


M


H
N N


SN-


Ar


ct


5-2a


5-2b (C2h)


R = t-Bu Ar = 1:


Figure 5-1 Schematic representation of A) cis- Azuleneone, 5-la, and its simplified derivative 5-
lb created for the calculations B) trans-Azuleneone,~trtrtr~r~r~ 5-2a, and its simplified
derivative 5-2b used in the calculations.









CHAPTER 6
MOLECULAR ORBITAL APPROACH FOR THE ELECTRONIC EXCITED STATES OF
CIS-AND 7RANS-AZULENEONE

6.1 Molecular Structures

All the calculations for 5-1b and 5-2b were performed with totally theoretical approach

without using any experimental data for the initial coordinates of the molecules. These planar

molecules are defined as cis- and trans-t~t~rt~t~rt~t~rt~ isomers of each other due to the positions of oxygens in

the structures. The symmetry point groups of 5-1b and 5-2b are Cs and C2h, respectively, as

depicted in Figure 5-1.

In Figure 6-1 the crystal structure of 5-la is shown. For simplicity hydrogen atoms have

been removed from the structure. Crystal structure of 5-2a is not available.

Experimental bond lengths (A+) for 5-la and calculated bond lengths (A+) for 5-1b are given

in Figure 6-2 and Figure 6-3, respectively. Hydrogen atoms have been removed from both of the

structures. The molecule is symmetric in solid state bearing a C2 aXiS so all the bond lengths are

being symmetrical for the experimental data.

When the calculated and experimental bond lengths for the cis isomer are compared, it is

seen that there is a good agreement between the values. The differences between the bond

lengths are smaller than 0.027 A+ except for the oxygen-carbon bond lengths. The mean absolute

deviation, |dl|, for the calculated and solid state bond lengths is 0.011A+. The deviations between

the experimental and calculated bond lengths are less than 2% error. For the case of oxygens

there is a higher deviation. The difference between the calculated and experimental bond length

for the carbonyl oxygen is 0.036 A+ which is around 2.85 % error. From these values it can be

concluded that there is a good correlation between the experimental and calculated bond lengths.

Since there is no crystallographic data for 5-2a, only the calculated bond lengths are

presented in Figure 6-4.










Calculated bond lengths for the trans isomer are very similar to those of cis isomer. This is

expected since the substituents on each side of the porphyrin core are the same. Both of the

molecules are highly conjugated xn-systems containing double and single bonds and the

calculated bond distances are in the expected interval for the single and double bond lengths.

In addition to bond lengths, calculated bond angles are also in good agreement with the

experimental data for 5-1b. Selected calculated and experimental angles inside the porphyrin

core for 5-1b are given in Table 6-1. Numbering scheme for the carbon atoms are given in Figure

6-5 for the cis isomer. The carbon atoms are labeled according to standard numbering for the

porphyrin core. For clarity, hydrogen atoms are removed.

Table 6-1. Selected experimental and calculated angles on the porphyrin core for 5-la and 5-1b.
Angle 5-la 5-1b
C20C1N1 125.8 125.2
NIC4C5 122.9 123.6
C4C5C6 124.9 125.0
C5C6N2 135.1 136.2
N2C9C 10 122.2 121.6
C9C10C11 121.0 123.0
C10C11N3 122.2 120.1
N3C14C15 135.1 138.4
C14C15C20 124.9 124.8
C15C16N4 122.9 122.2
N4C 19C20 125.8 125.0


6.2 Calculated Orbitals and the Spectra for the cis- and trans- Derivatives of Azuleneone

When the experimental and calculated spectra are compared there is a good agreement

between them. The Q band of the porphyrin is at 500 nm-600 nm region.139 The lowest energy

band for the 5-la is not around 600 nm but at 923 nm experimentally. There are two calculated

transitions for 5-1b, 1 A' and 2 A' at 1032.55 nm, and 915.83 nm, which are contributing to the

band in the experimental spectrum at the low energy region that has a maximum peak value at










923 nm. These calculated transitions are the split Q1 and Q2 bands, respectively as depicted in

Figure 6-6.

For the trans-Azuleneoner~r~r~r~r~r~ the lowest energy band is at 1100 nm experimentally. On the

calculated spectrum for the singlet states of 5-2b, this low energy is calculated to be at 1049.77

nm with 1 Bu symmetry. This Q band transition is mainly from HOMO to LUMO orbital. There

is a small contribution coming from HOMO-2 orbital for this transition as shown in Figure 6-7.

It is both experimentally and theoretically proved that both of the molecules are red

shifted, trans-Azuleneone being more red shifted than its cis isomer. It is clearly seen from the

Kohn Sham molecular orbital diagrams. The HOMO-LUMO energy gaps for these molecules are

calculated to be close to each other. The HOMO-LUMO gap for the cis isomer is slightly higher

than the trans isomer.

More red shifted trans-isomer~rtrtrtrt~t~t~ has its lowest energy transition with 76.60 % weight coming

from HOMO-LUMO interaction. On the other hand the lowest energy transition for the cis

isomer is 59.80% with HOMO-1-LUMO and 29.40% HOMO-LUMO interaction which makes

this transition relatively higher in energy.

These molecules are red shifted because xn-conjugation provided by the substituents on the

rings decrease the HOMO-LUMO energy gap with the electronic effects to the original

porphyrin ring. Detailed analysis of the four frontier orbitals shows these electronic effects

depending on the electron distributions. There have been several porphyrin systems reported in

the literature for the effects of the substituents for the red shift of the Q bands.94, 97, 98, 131, 140, 141-










In the literature it is also reported that with the increase of the size of the molecular

structure, Q band becomes more pure.131 This is also observed in our large molecules. All these

important results are discussed in detail in the following sections.

6.2.1 Kohn-Sham Orbitals

The energy levels of the orbitals of a porphyrin derivative are determined by the

substituents. The symmetry of the molecule with the substituents is responsible for the

redistribution of orbital coefficients.103 The ordering and the energy differences among the

molecular orbitals in addition to the strength of the configuration interaction coupling affect the

interaction of the four porphyrin orbitals.lor The Kohn Sham orbital diagram of some frontier

orbitals and the isoamplitude surfaces of their wave functions for both of the molecules are

shown in Figure 6-8 and Figure 6-9, respectively. Energies of some of the calculated frontier

molecular orbitals (MOs) are presented in Table 6-2.

Regarding the electronic transitions taking place for the UV-Vis spectra of the molecules,

the energy levels of the HOMO-1, HOMO, LUMO and LUMO+1 orbitals and the differences of

the energies between these orbitals have strong relevance for the interpretation of the spectra.

Due to the lowering of symmetry, LUMO and LUMO+1 orbitals are not degenerate.99 The

energy differences of the LUMO and LUMO+1 orbitals are 0.73 5 eV for the cis and 0.655 eV

for the trans isomer. It is clearly seen that the energies of LUMO and the LUMO+1 orbitals and

the LUMO-LUMO+1 energy differences of the two molecules are not very different from each

other. On the other hand, the energy differences of HOMO and HOMO-1 orbitals of the

molecules are not as close to each other. The HOMO-HOMO-1 energy differences for the cis

and transrt~t~rt~t~rt~t~rt~ isomers are 0.121 eV and 0.688 eV, respectively. The HOMO-LUMO gaps were

calculated to be 1.664 eV for 5-1b and 1.592 eV for 5-2b. These values indicate that the HOMO-










LUMO energy differences of the two molecules are very close to each other. The slight

difference of HOMO-LUMO gap and the fact that the transrt~t~rt~t~rt~t~rt~ isomer has the smaller HOMO-

LUMO gap support both the calculated and the experimental electronic absorption spectra of the

molecules. The lowest energy transition for the trans isomer, both on experimental and

calculated spectra, is lower than the one for the cis isomer which means that transrt~t~rt~t~rt~t~rt~ isomer is red

shifted more than the cis isomer. This can easily be seen in Figure 6-6 and Figure 6-7 which

show the calculated oscillator strengths plotted as a function of transition wavelength and the

experimental spectra being overlaid on the same plot for each of 5-1b and 5-2b, respectively.

Table 6-2. Calculated Molecular Orbitals, Symmetries and Energies (eV) for 5-1b and 5-2b.
5-1b 5-2b

MO Symmetry Energy (eV) Symmetry Energy (eV)

LUMO+4 a", -1.101 an -1.038

LUMO+3 a") -1.575 b, -1.529

LUMO+2 a", -2.593 an -2.593

LUMO+1 a", -2.727 b, -2.809

LUMO a", -3.462 b, -3.464

HOMO a", -5.126 an -5.056

HOMO-1 a", -5.247 an -5.744

HOMO-2 a", -6.104 b, -5.779

HOMO-3 a", -6.310 an -6.328

HOMO-4 a", -6.561 ag -6.602


Electron delocalizations on the orbitals are important for the interpretations of the

transitions in the excited state. In case of LUMO+1 orbitals, as seen in Figure 6-9, electrons are

localized on the porphyrin core for both the cis and transrt~t~rt~t~rt~t~rt~ isomers. The cis isomer has very small

participation of electrons on the phenyl groups which is a very slight difference from the










LUMO+1 orbital of the transrt~t~rt~t~rt~t~rt~ isomer. Unlike LUMO orbitals, unsubstituted nzeso carbon atoms

have high participation and substituted nzeso carbon atoms have no participation. When P-carbon

atoms are considered, there are high orbital amplitudes in each of the molecule. The nitrogen

atoms, however, have less amplitude when compared to LUMO orbitals. The main difference for

the LUMO+1 orbital of the cis isomer is that if we assume there is a hypothetical plane passing

through the substituted nzeso carbon atoms dividing the molecule into two halves as upper half

with both oxygen atoms and lower half without any oxygen atom, the participation for the

porphyrin ring in the upper half are higher than those in the lower half of the molecule. For the

trans isomer, since the oxygen atoms are located in a more symmetrical way, one in the upper

half and one in the lower part, the amplitudes on the porphyrin ring are not different from each

other for different halves of the molecule. It is clear that location of the oxygens affect the

electron localizations in LUMO+1 orbitals.

When LUMO orbitals are compared, there is an electron delocalization over the entire

molecule for each of the system. The amplitudes and the pattern of electron delocalizations on

the phenyl rings, seven membered rings, and on the porphyrin core are very similar for both of

the isomers. There is a nodal plane passing through the unsubstituted nzeso carbon atoms

observed for both of the LUMOs. On the other hand the amplitudes for the substituted meso

carbon atoms, P-carbon atoms and the nitrogen atoms are high for each of the isomer.

Considering HOMO orbitals, electrons are delocalized over the entire molecules in a

similar manner for the substituents and the porphyrin cores for both of the molecules. Both

molecules have high amplitudes on all of their nzeso carbon atoms and nitrogen atoms. Relatively

small participation on the phenyl rings on one side of the cis isomer brings the difference of the

electron distribution on the HOMO orbital when compared to that of the trains isomer. Electron










distribution for HOMO orbital of trains isomer is more homogenous than its cis analogue. This

must be due to higher symmetry of the transrt~t~rt~t~rt~t~rt~ isomer.

The biggest difference is observed with the HOMO-1 orbitals of the isomers. Electron

distribution for 5-1b is in such a way that, the part of the molecule that had only small

amplitudes for HOMO orbital now has high electron contribution for the case of HOMO-1

orbital. Similarly, the part of the molecule that had high amplitude now has very small

amplitude. The substituted meso carbon atoms have no electron distributions. Similarly the

participation on the substituted meso carbons for the transrt~t~rt~t~rt~t~rt~ molecule are very small, almost

negligible. The amplitudes on nitrogen atoms on HOMO-1 for 5-2b are much smaller when

compared to HOMO orbital of this molecule. HOMO-1 orbital of 5-2b shows electron

delocalization over the entire molecule, unlike 5-1b. Due to better distribution of the electrons,

distribution over a higher number of atoms, the stability of the bonds are improvedl45 and the

HOMO-1 orbital for 5-2b is more stabilized when compared to HOMO-1 orbital of 5-1b.

HOMO orbitals are more destabilized than HOMO-1 orbital since at the meso positions for

the HOMO orbitals, where the substitution is taking place; there are high amplitudes at meso

carbon. For the HOMO-1 orbitals these positions have very small amplitudes.97 According to

Gouterman's theorem99, 141 HOMO orbitals are accidentally degenerate with al, and atu

symmetries. The al, orbital has no amplitude at meso positions. It has very small participation at

the P-carbons. In case of atu Orbital there are high amplitudes on meso carbons and on nitrogens.

Therefore these molecules are susceptible for energy changes depending on the substituents. The

diagrams of HOMO orbitals reveal that for each isomer the porphyrin core keeps its atu type

character with high amplitudes at both the nitrogen atoms and meso carbon atoms. On the other

hand, especially for the transrt~t~rt~t~rt~t~rt~ isomer, HOMO-1 orbital keeps its alu type character.










Destabilization of the atu type orbital, (high participation at meso positions) with respect to alu

type of orbital (small participation at P-carbon atoms) for the porphyrin core is expected,103, 131,

140, 146 Since aromatic rings are fused into the porphyrin system through alternating meso

positions. Although alternating P-carbon atoms are also involved in substitution, due to their low

orbital participation, they would not make significant change for al,.

6.2.2 Excited States

In order to be able to interpret the experimental spectra for both cis- and trans-

Azuleneones, excited state calculations were carried out by TDDFT for the first fifteen singlet

excited states of 5-1b and 5-2b. The calculated oscillator strengths were plotted as a function of

transition wavelength for 5-1b and 5-2b are presented in Figure 6-6 and Figure 6-7, respectively,

as stated before. Experimental spectra of the molecules are overlaid on the same plots.

Calculated excited states with related symmetries, the weights of the transitions that have more

than 2% contributions to the excitations, transition energies and oscillator strengths for the cis

and trans isomers are given in Table 6-3.

6.2.2.1 Q-band regions for cis-Azuleneone and trans-Azuleneone

There is a good correlation between the experimental spectrum of 5-la and calculated

transitions of 5-1b. The two calculated singlet transitions at 1032.55 nm, and 915.83 nm with the

symmetries 1 A' and 2 A', respectively, are contributing to the band at the low energy region

with the maximum peak value at 923 nm for 5-1b.

These calculated transitions are split Q1 and Q2 bands, respectively. In order to verify this

interpretation, Gaussian broadening was applied to the calculated spectrum until the sum of the

individual Gaussian component peaks was in good agreement with the experimental spectrum.104,































704.71



616.33



580.01





503.37




501.87


501.21




499.09




469.69


457.70



445.37


0.0000 1.7593 1 A, H-1 ->L (80.40)
H ->L+2 (7.16)


0.0000 2.0117 2 A, H ->L+2 (86.20)
H-1 ->L (10.68)


0.1943 2.1376 3 Bu H-2->L (25.40)
H->L+1 (20.28)
H-3 ->L(18.08)
H-2 ->L+1(15.86)
H-8 ->L(3.24)

0.4747 2.4631 4 Bu H-3 ->L(51.80)
H-2 ->L+1(13.20)
H-2->L (9.20)
H ->L+1(6.80)
H-8 ->L(2.98)
0.0000 2.4704 3 A, H-1 ->L+1(88.80)
H-6 ->L(4.06)

0.0000 2.4737 1 B, H-4 ->L(84. 18)
H-5 ->L+2 (9.20)



0.0000 2.4842 'An H-5 ->L(83.40)
H-4 ->L+2(9.70)



0.0000 2.6397 4 A, H-6 ->L(38.18)
H-2->L+2(36.18)
H-7->L(16.74)
0.0866 2.7088 5 Bu H-1->L+2(51.40)
H-2 ->L+1(24.00)
H-3->L (10.66)
H->H+3(5.26)
0.0000 2.7838 5 A, H-4->L+2(53.60)
H-6 ->L(22.60)
H-7 ->L(13.54)


147 Figure 6-10 and Figure 6-11 show the Gaussian broadening curves with the actual spectra


overlaid for 5-1b and 5-2b, respectively. It was clearly seen from the Gaussian broadening


Table 6-3. Calculated electronic excited states, orbital configurationSa, b (% Weight), transition
energies and oscillator strengths for the first fifteen singlet states for 5-1b and 5-2b.
5-1b 5-2b


h (nm) Oscillator Energy Exc.St Orbital
Strength (eV) ate Contributionb
(f) (Weight %)
1032..55 0.0109 1.2007 1A' H-1->L (59.80)
H ->L (29.40)
915.83 0.1161 1.3538 2 A' H-1 >L(28.40)
H ->L (43.60)
H-1->L+2 (6.40)
H-1 ->L+1(4.80)
H->L+1 (4.44)
634.12 0.0266 1.9552 3 A' H ->L+1 (55.20)
H-2 ->L (23.74)
H->L+3 (9.00)
H-1->L+3 (6.04)
608.38 0.0042 2.0379 4 A' H->L+2 (51.40)
H-1>L+1(32.40)
H->L+1 (4.38)
H-1->L+2 (3.72)
584.45 0.0133 2.1214 5 A' H-1 >L+1(31.60)
H->L+2 (28.20)
H-1 >L+2(20.66)
H-2 ->L+1(6.76)
H-3->L+1 (4.52)
H ->L+1 (3.66)
533.86 0.2326 2.3224 6 A' H-1 >L+2(44.60)
H-3->L (32.40)
H-1 ->L+1(4.10)
H-2->L (3.36)
H ->L+2 (2.28)
505.30 0.0000 2.4536 1 A" H-5 ->L (83.00)
H-5 ->L+1(6.88)
H-5 ->L+2(5.38)
502.69 0.2349 2.4664 7 A' H-3 ->L (42.00)
H-2 ->L (11.18)
H-1 >L+1(10.48)
H-7 ->L (10.30)
H-2 ->L+1(4.34)
496.70 0.3321 2.4961 8 A' H-2 ->L (37.74)
H ->L+2 (16.58)
H-1->L+2 (5.12)
H-3 ->L (4.64)
H-2 ->L+1(4.20)
460.40 0.1156 2.6930 9 A' H-4 ->L (4.60)
H-3->L+1 (2.40)

453.03 0.0000 2.7368 2 A" H-8>L+1(78.80)
H-8->L+2 (6.68)
H-8->L+1 (6.60)

447.58 0.1253 2.7701 10 A' H-7 ->L (47.60)
H-6 ->L (28.88)
H-4 ->L (4.10)


h (nm) Oscillator Energy Exc. Orbital
strength (eV) State Contributionb
(f) (Weight %)
1049.77 0.0881 1.1811 1 Bu H >L(76.60)
H-2 ->L+1(6. 18)
710.49 0.0008 1.7450 2 Bu H ->L+1 (53.80)
H-2 ->L (46.80)


















442.32 0.1072 2.8030 11 A' H-6 ->L (59.20) 440.44 0.0583 2.8150 6 Bu H- 8 ->L(71.20)
H-7 ->L (26.12) H-11 ->L(7.90)
H-2 ->L+1(4.86) H-3 ->L+1(5.56)
414.41 0.0515 2.9918 12 A' H->L+3 (60.34) 440.42 0.0000 2.8151 6 A, H-7 ->L(62.14)
H-2>L+1(28.60) H-6 ->L(26.40)
H-2->L+2 (4.68)
400.43 0.0251 3.0962 13 A' H-3 >L+1(66.00) 431.20 0.0172 2.8753 7 Bu H-9 ->L(50.14)
H-1 >L+3(15.18) H-1 ->L+2(15.00)
H-2 ->L+2(5.84) H ->L+3(11.40)
H-8 ->L(5.36)
H-2 ->L+1(5.14)
aHOMO-1, HOMO, LUMO and LUMO+1 orbitals are represented as H-1, H, L and L-1 respectively.
bConfigurations which contribute more than 2 % are shown.

analysis that these peaks do not resolve in the spectrum, instead add up and together contribute to

a broad peak. Therefore it is clear that these peaks are contributing to the absorption peak in the

experimental spectrum at 923 nm. The calculated splitting energy, AQ/cm- for Q1 and Q2

bands is 1234.3. For the symmetrically ring expanded porphyrin metal free species it was

reported that for the split Q bands, the intensity of the one in the lower energy is lower than the

one in the higher energy.131It is the case for 5-1b as can be seen from Table 6-3. The calculated

intensity of higher energy Q2 band is 0. 1161 and that of lower energy Q1 band is 0.0109. The

intensity ratio for Q2/Q1 is 10.65.

Considering the orbital contributions for 1 A' and 2 A', it is seen that both of the

transitions are mainly from HOMO-1 and HOMO orbitals to LUMO orbital. There are also small

contributions for 2 A state coming from HOMO-1 to LUMO+1, HOMO-1 to LUMO+2 and

HOMO to LUMO+1 transitions. Electronic transition for 1 1A is the linear combination of two

configurations from HOMO-1 to LUMO and HOMO to LUMO orbitals with 59.80 and 29.40 %

weights, respectively. Similarly the transition for 2 A is mainly the linear combination of

HOMO-1 to LUMO and HOMO to LUMO configurations with 28.40 and 43.60% weights in the


Table 6-3. Continued
5-1b

h (nm) Oscillator Energy Exc.St Orbital
Strength ate Contributionb
(f) (eV) (Weight %)


5-2b

h (nm) Oscillator Energy Exc. Orbital
strength State Contributionb
(f (eV)
(Weight %)










same order. Therefore the two transitions are the linear combinations of the orbitals with the

same configurations. Basically, the coefficients which are the weights of the configurations are

interchanged. This configuration behavior of the two states indicates the mixing of these two

excited states. Actually HOMO to LUMO configuration of 1 A' (29.40%) and HOMO to

HOMO-1 configuration of2 A' (28.40%) are mixing with opposite signs, -0.3843 and 0.37664

respectively, according to the computational data. A similar case for the mixing of configurations

for the two excited states was reported in the literature for a porphyrin isomer with Cs symmetry.

The explanation for the mixing of the excited states was that it was originating from symmetry

lowering of the molecular structures from D~h of porphyrin to lower Cs symmetry.148 More Cs

symmetric porphyrin derivatives with split Q bands have been reported in the literature.131, 149 As

a result in our system configuration interaction between the orbitals are enhanced and caused the

splitting of the Q bands in the calculations which may be due to the lowering of the symmetry of

the molecule. Although the substituents and the lowering of the symmetry affected both the

electronic energy terms and the energies of the orbitals, splitting is not caused by the change in

the orbital energies, but is caused by the electronic energy terms.150

As mentioned before, the lowest energy transition in the experimental UV-Vis spectrum of

trans-Azuleneoner~r~r~r~r~r~ is at 1100 nm. The lowest transition energy is calculated to be at 1049.77 nm

with 1 Bu symmetry for 5-1b. This Q band transition is mainly from HOMO to LUMO orbital

with a small contribution coming from HOMO-2 orbital. The strong contribution of HOMO-1

orbital is seen for the forbidden transition for 1 A, state at 704.71 nm with 80.40% weight for

HOMO-1 to LUMO transition. There is another transition calculated at 704.71 nm with 1Bu.

Considering the fact that 2 Bu state is almost 50% mixed with the configuration of HOMO-2, it

can not be considered as pure Gouterman type transition. There are cases reported in the










literature that transitions originating from low lying orbitals to the LUMO and LUMO+1 orbitals

taking place between the Q band and the B bands." Basically, the low energy transitions for Q

bands of the molecules are originated from HOMO-LUMO and HOMO-1-LUMO interactions

for the cis isomer and HOMO-LUMO interaction for the transrt~t~rt~t~rt~t~rt~ isomer. The differences

originating between the molecules are that HOMO-1-LUMO contribution for trans isomer is

forbidden and it is at higher energy. The reason for this situation is that for both of the molecules

the energies of the LUMO+1, LUMO and HOMO orbitals have very similar energy values. The

only difference is coming from the energy of HOMO-1 orbital of transrt~t~rt~t~rt~t~rt~ isomer, which is more

stabilized than that of cis isomer. The stabilization energy with respect to HOMO-1 orbital of cis

isomer is 0.532 eV. The reason for this is that for 5-2b the electrons are delocalized all over the

molecule for HOMO-1 orbital but for the cis isomer that is not the case and HOMO-1 orbital is

destabilized more.

6.2.2.2 B-band regions for cis-Azuleneone and trans-Azuleneone

When the rest of the spectrum for the cis isomer is considered, it is seen that there is a

shoulder at 879 nm. In that region there is no singlet transition calculated. This shoulder must be

due to vibrational transitions. The transitions calculated at 634.12 nm, 608.38 nm, and 584.45 nm

contribute to shoulders at 644 nm and 590 nm at UV-Vis spectrum. The peaks calculated at

533.86 nm and 502.69 nm are contributing to the peak at 547 nm which has the highest

absorbance in the experimental UV-Vis spectrum. The highest oscillator strength calculated for

the singlet transitions is at 496.70 nm. The calculated peaks at 460.40 nm, 447.58 nm, and

442.37 nm correspond to the experimental peak at 450 nm. The calculated peaks at 414.41 nm

and 400.43 nm are also in good agreement with the experimental data.










The small peak at 762 nm observed on the experimental spectrum 5-2b might be coming

from the contribution from the calculated transition at 710.49 nm. Experimentally the band with

the highest absorbance value is at 580 nm and the peak calculated at 580 nm contributes to this

band. The band with lower absorption value at 535 nm on the UV-Vis spectrum is calculated to

be at 503 nm. The shoulder at 475 nm should be corresponding to the transition calculated at

457.70 nm. The transitions calculated at 440.42 nm and 431.20 nm are contributing to the peak at

427 nm on the experimental spectrum.

The small peak at 850 nm is probably coming from vibrational transitions. The shoulder at

1220 nm (8196.72 cm ) for the broad band with 3Lax at 1100 nm (9090.91 cm ) must be coming

from the vibrational transitions. The difference of energy between these two points is 894. 19 cm

1.The deviations between the calculated and experimental spectra are in acceptable range which

is an indication of good agreement between the two spectra.

When the B-band regions of both of the molecules are considered, they both show similar

trend. The region between between 400 nm and 600 nm has the peaks related to B-band

transitions for both of the molecules. The peaks are broad and split. This is due to lowering of

symmetry and the complexities of the structures. Molecular symmetry affects the splitting of the

Soret bands." As presented on Table 6-3 for the B band, large number of occupied and

unoccupied orbitals besides HOMO-1, HOMO, LUMO, LUMO+1 are highly contributing to the

transitions. As a result it is not possible to predict the pure Soret band transitions for these

molecules. Similar cases have been reported in the literaturel29 and explained that Gouterman

model is a simple model and it does not provide explanation for the complexity of the Soret

band. Therefore it is suggested that more transitions, allowed and/or forbidden, should be

calculated.152










6.2.2.3 Oscillator strengths

Comparison of the calculated and experimental oscillator strengths is more complicated

due to some important error sources. Unless solvation effect is included in the calculations, the

comparison will be between the experimental data taken in solution and computed data

calculated in the gas phase which is the situation in this work. Solvation effect may cause

deviations from the expected results and such cases are reported in the literature.94, 153

The difficulty in the comparison of experimental and calculated data rises from the overlap

of the electronic band with the neighboring electronic or vibronic bands.148 Overlap of these

bands creates long tails that makes the spectral band integration difficult for the prediction of

experimental oscillator strengths from

f = 3.32 x 10-9 1e (u) do,

where the extinction coefficient a has the unit of molel cm-l and the wave number u is in

cm- This equation is approximated as it is shown below by using a single Gaussian to represent

the band shape.

f = 3.32 x 10-9 (Au/ 6) 2 du = 3.32 x 10-9 nemax8

In the equation 6 is the half-width at a = Emax/e which relates the full-width (h) at half-

maximum by h = 2(In2)o.56. Band shape approximation and band overlap are not the only error

sources. The equations for the oscillator strength given above neglect the solvent refractive index

correction. This may cause 10 to 20 percent error for common solvents.15 As a result of all these

error sources it is almost impossible to determine the actual oscillator strength for the

experimental spectrum and in this work experimental and theoretical oscillator strengths are not

compared.










6.3 Conclusion

In this study, DFT level computational calculations for the molecular orbitals and the

singlet excited state calculations were performed for the expanded porphyrin derivatives cis- and

trans-Azuleneone.~trtrtr~r~r~ The experimental and calculated structures and the spectra were compared

and it was determined that they showed good agreement. By using Gouterman's theory and the

calculated molecular orbitals and calculated singlet excited states of the molecules, the electronic

spectra of the molecules were analyzed from the view of theory. According to both experimental

and computational data trans isomer has more red shifted band relative to its cis analogue due to

xn- conjugation.


Figure 6-1 Crystal structure of 5-la.















7-3 '-475 N

U1 w 1.373



O r






Figure 6-2 Experimental bond lengths for 5-la.


O









7


co 1.69 7~: SO t

1.382 u

83s
2.3_46_b

N ft 31


-449 .


1.389

1.60 h

7.40




37


Figure 6-3 Calculated bond lengths for 5-1b.



















P
ul
h) n3
U1 h
~p~ 7 2 .D~i0~
Q~ ~ ~g
a
CO h)
1~N
az~
ZJ~ 7~6~9~
`~3~

Figure 6-4 Calculated bond lengths for 5-2b.


Figure 6-5 Numbering scheme for the cis isomer for the selected atoms.









121















1.2


1

















10.2











40500 600 700 800 9003 1000X 1100 12010 1300 1400

Wavelength (nm)

Figure 6-7 Experimental and calculated electronic spectra for 5-2b.

















b


a"-

a" -


a"
a" -


a,


by, -LUMO






;4u -HN\
b-r
I9


~a"-LUMO





a" HOO

a"

a"-


5-16 5-2b
0, C;2
Figure 6-8 Kohn Sham orbital energy diagrams for some of the frontier orbitals of 5-1Ib and 5-2b,
respectively.























123












LUMO+2


LUMO+1





LUMO





HOMO





HOMO-1


HOIMO-2


5-2b


5-1b


Figure 6-9 Isoamplitude surfaces of the wave functions of 5-1Ib and 5-2b for some of their
frontier orbitals, respectively.

















1.2-


I rr~-Gaussian Brodening Curve
0. Obtained for the Calculated
% Data
S0.6 Actual Uv-Vis Spectrum



0.2-


400 600 800 1000 1200 1400 1600 1800
Wavelength (nm)

Figure 6-10 Gaussian broadening curve and the actual Uv-Vis spectrum for the cis isomer.














0 .8 I -Gaussian Broadening Curie
C I IIObtained for the Calculated
0. Data
II IlI II Actual Uw-Vis Spectrum




0.0

400 600 800 1000 1200 1400 1600 1800
Wavelength (nm)

Figure 6-11 Gaussian broadening curve and the actual Uv-Vis spectrum for the transrt~t~rt~t~rt~t~rt~ isomer.









CHAPTER 7
SUMMARY

Nuclear waste is created every day in nuclear reactors. The waste contains highly

radioactive actinides with very long half lives. In order to be able to convert them into shorter

living nuclide transmutation is necessary. However it is not possible in the present conditions

because lanthanides are present in the waste mixed with the actinides and they interfere with the

transmutation processes by neutron capture. This makes transmutation of actinides impossible.

As a result it is important to separate these two chemically similar metal cations from each other.

For that purpose we worked with a new C3 Symmetric ligand system bearing both pyridine and

diamide groups together that also takes advantage of reorganization to provide a good

coordination site for the metal. Extraction data reveal that, ligands with the lower side

functionalized triphenoxymethane platform are working efficiently for the extractions of

lanthanide cations when the extraction experiments were performed in the presence of COSAN.

The N\MR scale extraction data clearly shows the extraction with the formation of a C3-

symmetric species in the solution. At a certain concentration ratio of the ligand with COSAN and

the lanthanide Lu, the extraction is 100 % efficient in the NMR timescale. Also solid state

structures of the metal complexes with the upper side functionalized triphenoxymethane platform

confirm the complexation of the ligand from its carbonyl and nitrogen binding sites. Our data

with lanthanides indicate that this ligand system is a promising ligand system for future

application which is consistent with the recently reported data with the same derivative.

Due to interesting spectroscopic properties of porphyrins and limited research in the

expanded porphyrin systems we were interested in the computational calculations for two

expanded porhyrin derivatives cis- and trans-azuleneoner~r~r~r~r~r~ to be able interpret their electronic

spectra. For this purpose DFT level computational calculations have been performed successfully









for these molecules with their corresponding point groups. Calculated and experimental

geometries for the cis- isomer are comparable. Calculated excited states are consistent with the

experimental spectra. The cis isomer shows split Q band region because HOMO-1 to LUMO and

HOMO-LUMO configurations show configuration interaction. This is due to electronic affects of

the substituents and symmetry lowering. For the B-band region of the spectra for both molecules,

there are contributions coming from lower lying orbitals as a result of which more transitions are

observed. Both experimentally and theoretically it has been confirmed that both of the molecules

are red shifted due to 2n- conjugation. HOMO-LUMO gap for trans-isomer is slightly lower so it

is more red shifted than its cis analogue. This study has been one of the most detailed

computational studies performed on expanded porphyrin systems. The data was successfully

interpreted with respect to molecular orbital approach in relevant with Gouterman's theory for

the porphyrin systems.










APPENDIX A
EXTRACTION DATA


Extraction Data for 2-10:




100
90
80
70
60
%E
50
40


La Ce Pr Nd Eu Gd Tb Dy Er Tm Yb


Lanthanides


Figure A-1 Extraction plot for 1x10-3 M 2-10 in CH2 12 with 1x10-4 M Lanthanides in 1 M
HNO3 .


Table A-1 Extraction data for Figure A-1.


E%
Error
2.0


6
0.003647
0.002635
0.002427
0.006619
0.003502
0.001762
0.001201
0.004004
0.001518
0.001677
0.000681


D
0.145014
0.170899
0.17
0.164319
0.123725
0.086409
0.086556
0.188371
0.18801
0.205788
0.165751


E %
13
15
15
14
11
8
8
16
16
17
14















100
90
80
70
60
%E
50
40
30
20
10 rl

La Ce Pr Nd Eu Gd Tb Dy Er Tm Yb

Lanthanides
Figure A-2 Extraction plot for the second extraction for 1x10-3 M 2-10 in CH2 12 with 1x10-4 M
Lanthanides in 1 M HNO3.


Table A-2 Extraction fata for Figure A-2.


E%
Error
1.1
1.2
0.9
0.4
1.0
0.9
1.1
3.7
0.7
2.3
0.9


D
0.135255
0.061197
0.093917
0.085267
0.085917
0.098098
0.088106
0.137533
0.10508
0.133104
0.128057


E%
12
6
9
8
8
9
8
12
10
12
11


6
0.001922
0.002194
0.001668
0.00085
0.002003
0.001801
0.002329
0.007212
0.001405
0.003971
0.001477
















100
90
80
70
60
%E 50

40
30
20
10
10


La Ce


Pr Nd Eu Gd Tb
Lanthanides


Dy Er Tm Yb


Figure A-3 Extraction plot for the third extraction for 1x10-3 M 2-10 in CH2 12 with 1x10-4 M
Lanthanides in 1 M HNO3.


Table A-3 Extraction data for Figure A-3.


E%
Error
0.5
0.1
0.5
0.6
0.4
0.1
0.5
0.8
0.5
1.2
1.5


6
0.000849
0.000208
0.000981
0.001118
0.000763
0.000153
0.001012
0.001501
0.000949
0.002021
0.002287


D
0.073389
0.072376
0.076271
0.094292
0.085258
0.081001
0.090026
0.090724
0.10679
0.091616
0.11978


E %
7
7
7
9
8
7
8
8
10
8
11


mmmI mHAHA


















100
901
80
701
601
%E
501
401
30
20
10
10


La Ce Pr Nd Eu Gd Tb Dy Er Tm Yb
Lanthanides
Figure A-4 Extraction plot for 7.63x10-3 M 2-10 in CH2 12 with 1x10-4 M Lanthanides in 1 M
HNO3 .






Table A-4 Extraction data for Figure A-4.


E%
Error
0.6
2.7
0.4
1.1
0.8
1.3
0.7
0.8
2.3
0.8
0.6


D
0.058993
0.046717
0.089955
0.060275
0.061268
0.063
0.060358
0.069477
0.118654
0.041243
0.079088


E %
6
4
8
6
6
6
6
6
11
4
7


6
0.001172
0.005186
0.000757
0.002159
0.001552
0.002658
0.001353
0.001662
0.004366
0.001473
0.001044


M mT. M M M M M M E m M





























T m r


100
90
80
70
60
%E 50
40
30
20
10
0
-10


La


Ce Pr Nd EuGd Tb Dy


Er Tm Yb


Lanthanides

Figure A-5 Extraction plot for 1x10-3 M 2-10 in 1-Octanol with 1x10-4 M Lanthanides in 1 M
HNO3 .








Table A-5 Extraction data for Figure A-5.


E%
Error
0.9
0.7
3.8
0.2
0.5
1.0
0.1
0.4
0.8
1.0
1.4


D
-0.03556
-0.03205
-0.00196
-0.03465
-0.05016
-0.03544
-0.02526
-0.02143
0.003156
0.01445
0.023555


E %
-4
-3
0
-4
-5
-4
-3
-2
0
1
2


6
0.00165
0.001212
0.007151
0.000473
0.00105
0.002021
0.000252
0.000757
0.001473
0.001735
0.00215














100
90
80
70
60

%E 50
40
30
20
10
0
-10


La


Ce Pr Nd Eu Gd Tb Dy Er Tm Yb

Lanthanides


Figure A-6 Extraction plot for 1x10-2 M 2-10 in 1, 2-dichloroethane with
lx10-4 M Lanthanides in 1 M HNO3.


1x10-3 M COSAN with


Table A-6 Extraction data for Finure A-6.


E%
Error
N/A
0.1
N/A
0.1
0.6
N/A
0.2
N/A
N/A
0.1
0.6


E %
N/A
0
N/A
0
0
N/A
1
N/A
N/A
7
8


N/A
0.004431
N/A
0.004873
0.00483
N/A
0.01404
N/A
N/A
0.079635
0.086155


N/A
0.000231
N/A
0.000153
0.001069
N/A
0.0004
N/A
N/A
0.000153
0.000987


mM












































6
0.002364
0.003581
0.008262
0.006281
0.000839
0.005216
0.003453
0.004521
0.001582
0.0009
0.001735


$ mTm M a .m &


Extraction Data for 2-11:


-


100
90
80
70
60
i 50
40
30
20

100

-10


La


Ce


Pr Nd Eu Gd Tb Dy Er


Tm Yb


Lanthanides


1x10-3 M 2-11 in CH2 12 with 1x10-4 M Lanthanides in 1 M


Figure A-7 Extraction plot for
HNO3 .


Table A-7 Extraction Data for Finure A-7.


E%
Error
1.3
1.9
4.4
3.2
0.4
2.6
1.7
2.3
0.8
0.5
1.1


D
0.075269
0.038589
0.083124
0.06983
0.062891
0.051791
0.009059
0.072717
0.043338
0.033668
0.051034


E %
7
4
8
7
6
5
1
7
4
3
5
































-~T~~I~Ll~ill


Extraction Data for 2-12:


100
90
80
70
60
%E
50
40
30
20
10
0


La Ce Pr Nd Eu Gd Tb Dy Er Tm Yb
Lanthanides

Figure A-8 Extraction plot for 1x10-3 M 2-12 in CH2 12 with 1x10-4 M Lanthanides in 1 M
HNO3 .


Table A-8 Extraction data for Figure A-8.


E%
Error
0.9
2.3
0.9
0.3
1.1
0.5
0.2
0.8
0.1
0.4
0.4


E %
3
4
5
4
7
3
5
4
2
2
4


6
0.001601
0.004444
0.001716
0.000643
0.002329
0.001172
0.000404
0.001652
0.0003
0.0007
0.000577


0.031274
0.043884
0.051061
0.037865
0.080184
0.028457
0.055407
0.046512
0.022731
0.020428
0.046141
































La Ce Pr Nd Eu Gd Tb Dy Er Tm Yb


100
90
00
70
60
%E
50
40
30
20
10


Lanthanides
Figure A-9 Extraction plot for the second extraction for 1x10-3 M 2-12 in CH2 12 with 1x10-4 M
Lanthanides in 1 M HNO3.






Table A-9 Extraction data for Figure A-9.


E%
Error
1.1
0.7
1.1
1.2
0.4
0.6
0.5
1.8
0.3
1.8
2.7


E %
1
1
4
1
4
4
3
1
-1
0
0


6
0.002043
0.001405
0.002157
0.002411
0.000814
0.00132
0.001115
0.003544
0.000557
0.003291
0.004405


D
0.009649
0.007234
0.039457
0.010294
0.043686
0.039487
0.026457
0.01436
-0.01002
-0.00131
0.003877






























~~~LILILIIL


Extraction Data for 2-13:


100
90
80
70
60
%E
50
40
30
20

10


La Ce Pr Nd Eu Gd Tb


Er Tm Yb


Lanthanides

Figure A-10 Extraction plot for 1x10-3 M 2-13 in CH2 12 with 1x10-4 M Lanthanides in 1 M
HNO3 .





Table A-10 Extraction data for Figure A-10.


E%
Error
3.6
1.8
1.1
1.7
0.6
1.5
0.6
3.0
0.7
1.3
3.0


D
0.12111
0.059809
0.07676
0.070052
0.052965
0.0729
0.068024
0.108818
0.114496
0.129527
0.103874


E %
11
6
7
7
5
7
6
10
10
11
9


6
0.006345
0.003291
0.00206
0.003232
0.001136
0.003024
0.001127
0.005987
0.001277
0.002248
0.004676

















90
80
70
%E 0
50
40
30
20
10

La Ce Pr Nd Eu Gd Tb Dy Er Tm Yb

Lanthanides

Figure A-11 Extraction plot for the second extraction for 1x10-3 M 2-13 in CH2 12 with 1x10-4 M
Lanthanides in 1 M HNO3.


Table A-11 Extraction data for Figure A-11.


E%
Error
1.9
1.1
0.9
0.5
1.0
1.3
0.8
0.9
1.3
1.7
1.8


D
0.083299
0.075311
0.063429
0.085338
0.071954
0.087781
0.058083
0.076503
0.092951
0.10835
0.12503


E %
8
7
6
8
7
8
5
7
9
10
11


6
0.003444
0.001955
0.001609
0.001012
0.001922
0.002702
0.001637
0.001838
0.0024
0.002821
0.002715













100
90
80
70
60
%E 50
40
30


La Ce Pr Nd Eu Gd Tb Dy Er Tm Yb
Lanthanides

Figure A-12 Extraction plot for the third extraction for 1x10-3 M 2-13 in CH2 12 with 1x10-4 M
Lanthanides in 1 M HNO3.


Table A-12 Extraction data for Figure A-12.


E%
Error
4.2
2.3
0.7
2.3
0.5
2.1
0.7
1.0
2.8
0.2
0.4


D
0.119228
0.167633
0.121535
0.117693
0.117399
0.164662
0.096446
0.125714
0.145987
0.180952
0.165915


E %
11
14
11
11
11
14
9
11
13
15
14


6
0.007495
0.004243
0.00121
0.004349
0.000945
0.004382
0.00135
0.002022
0.005233
0.000361
0.000693































E %
85
86
89
85
80
78
78
71
71
63
68


6
0.000513
0.000462
0.00245
0.003083
0.006735
0.007146
0.010615
0.000764
0.004518
0.007749
0.001769


III


r


100
90
80
70
60
YoE
50
40
30
20
10
0


I I


IIIII


La Ce Pr Nd Eu Gd Tb Dy Er Tm Yb
Lanthani-des
Figure A-13 Extraction plot for 1x10-4 M 2-13 in 1, 2-dichloroethane with 1x10-3 M COSAN
with 1x10-4 M Lanthanides in 1 M HNO3.


Table A-13 Extraction data for Figure A-13.


E%
Error
0.3
0.3
1.3
1.6
3.5
3.5
5.2
0.4
2.4
4.6
1.1


D
5.792357
5.983312
7.9328
5.784959
3.957447
3.470418
3.608859
2.476471
2.47424
1.691371
2.13266














100
90
80
70
60
%E
50
40
30
20

10

La Ce Pr Nd Eu Gd Tb Dy Er Tm Yb
Lanthanides

Figure A-14 Extraction plot for the second extraction for 1x10-4 M 2-13 in 1, 2-dichloroethane
with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M H~NO3.


Table A-14 Extraction data for Figure A-14.


E%
Error
0.9
0.5
1.0
0.5
1.8
0.5
0.6
6.2
0.5
14.3
1.6


D
7.042324
12.07993
7.336691
6.597772
8.7344
3.166586
5.003693
4.824602
6.123995
6.590986
4.77633


E %
88
92
88
87
90
76
83
83
86
87
83


6
0.001704
0.000872
0.001893
0.001041
0.00363
0.001044
0.001353
0.012831
0.001041
0.026872
0.002857






































6
0.002386
0.003242
0.001343
0.002706
0.007411
0.003297
0.009782
01008433
0.004654
0.011692
0.004693


I IIIII


100
90
80
70
60
YoE
50
40
30
20
10
0


rm


La Ce Pr Nd Eu Gd Tb Dy Er Tm Yb
Lanthanides
Figure A-15 Extraction plot for the third extraction for 1x10-4 M 2-13 in 1, 2-dichloroethane with
lx10-3 M CO SAN with 1x10-4 M Lanthanides in 1 M HNO3.


Table A-15 Extraction data for Figure A-15.


E%
Error
1.3
1.7
0.7
1.3
3.7
1.5
4.5
4.1
2.3
6.2
2.7


D
7.255523
6.896304
7.348703
6.645081
3.820919
4.424473
4.243548
3.227088
2.173913
4.02852
3.639581


E %
88
87
88
87
79
82
81
76
68
80
78

















- -

-

-

-

-

-

-

-

-


100

90

80

70

60
%E
50

40

30

20

10

0


La Ce Pr Nd Eu Gd Tb Dy Er Tm Yb

Lanthanides
Figure A-16 Extraction plot for 1x10-3 M 2-13 in 1, 2-dichloroethane with 1x10-3 M COSAN
with 1x10-4 M Lanthanides in 1 M HNO3.


Table A-16 Extraction data for Figure A-16.


E%
Error
0.2
0.5
0.1
0.6
0.2
0.7
0.3
1.1
2.1
0.9
2.2


D
2.578523
12.23601
24.72811
25.60829
19.01718
8.561728
16.29296
66.93103
6.838936
4.738149
4.371824


E %
72
92
96
96
95
90
94
99
87
83
81


6
0.000321
0.000985
0.000252
0.001159
0.000458
0.00148
0.000603
0.002138
0.003923
0.001557
0.00335




































6
0.003166
0.001136
0.003696
0.009828
0.002696
0.000551
0.02011
0.00412
0.009037
0.02556
0.031988


I IIIII


100
90
80
70
60
%E
50
40
30
20
10
0


IIli


La Ce Pr Nd Eu Gd Tb Dy Er Tm Yb
Lanthanides
Figure A-17 Extraction plot for the second extraction for 1x10-3 M 2-13 in 1, 2-dichloroethane
with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3.



Table A-17 Extraction data for Figure A-17.


E%
Error
1.7
0.6
1.9
4.8
1.3
0.3
9.4
2.0
4.4
13.8
18.7


D
1.675842
6.427606
8.72621
3.753679
7.958333
15.05941
4.580183
14.25616
2.383899
1.953846
3.521108


E %
63
87
90
79
89
94
82
93
70
66
78












Extraction Data for 2-14:


100
90
80
70
60
%E
50
40
30
20

10

La Ce Pr Nd Eu Gd Tb Dy Er Tm Yb
Lanthanides
Figure A-18 Extraction plot for 1x10-3 M 2-14 in 1, 2-dichloroethane with 3x10-3 M COSAN
with 1x10-4 M Lanthanides in 1 M HNO3.


Table A-18 Extraction data for Figure A-18.


E%
Error
0.7
3.6
0.7
4.0
7.9
2.5
1.4
2.5
7.8
0.1
3.8


5534.75
22.48742
6.294494
14.94819
10.5239
2.744684
5.148112
2.445022
3.688668
1.995948
1.286418


E %
100
96
86
94
91
73
84
71
79
67
56


6
0.001258
0.00678
0.00132
0.008278
0.015915
0.005359
0.002937
0.005125
0.015698
0.0001
0.006294










Extraction Data for 2-15:


100
90
80
70
60
50
%E
40
30
20
10
0


-20


Lanthanides
Figure A-19 Extraction plot for 1x10-3 M 2-15 in 1-Octanol with 1x10-4 M Lanthanides in 1 M
HNO3 .


Table A-19 Extraction data for Figure A-19.


E%
Error
2.3
0.5
0.3
0.2
0.1
0.9
0.1
0.8
0.3
0.4
0.1


D
-0.06512
-0.01518
-0.01526
-0.03367
-0.023
-0.02529
-0.02991
-0.01953
-0.01744
-0.02124
-0.02323


E %
-7
-2
-2
-3
-2
-3
-3
-2
-2
-2
-2


6
0.004244
0.000981
0.000557
0.000458
0.000252
0.001973
0.000173
0.001677
0.000666
0.000666
0.0002


3kI r I _I gu le-- -





























m gIgg -
La Ce Pr NJa Eu GJ TU y ElI TrnlY


100
90
80
70
60
50
E%
40
30
20
10
0
-10
-20


Lanthanides

Figure A-20 Extraction plot for the second extraction for 1x10-3 M 2-15 in 1-Octanol with 1x10-4
M Lanthanides in 1 M HNO3.





Table A-20 Extraction data for Finure A-20.


E%
Error
0.3
1.4
1.2
1.2
0.4
0.6
0.3
0.9
0.6
0.6
0.9


D
-0.03686
-0.05748
-0.04829
-0.0535
-0.0601
-0.05457
-0.0658
-0.0543
-0.02391
-0.01312
-0.02137


E %
-4
-6
-5
-6
-6
-6
-7
-6
-2
-1
-2


6
0.000529
0.002598
0.002272
0.002476
0.000737
0.001222
0.0006
0.001888
0.001229
0.001124
0.00155































La Ce Pr Nd EuG Tb Dyl Er Tm Yb


100
90
80
70
60
50
%E
40
30
20
10
0
-10
-20


Lanthanides

Figure A-21 Extraction plot for the third extraction for 1x10-3 M 2-15 in 1-Octanol with 1x10-4
M Lanthanides in 1 M HNO3.


Table A-21 Extraction data for Figure A-21.


E%
Error
1.0
0.8
0.2
0.2
0.3
0.2
0.9
0.4
0.3
1.3
0.1


D
-0.04782
-0.04641
-0.03401
-0.0259
-0.02394
-0.03599
-0.02825
-0.02574
-0.02414
-0.02892
-0.04223


E %
-5
-5
-4
-3
-2
-4
-3
-3
-2
-3
-4


6
0.001848
0.001626
0.000473
0.000403
0.000613
0.000473
0.001966
0.000777
0.000661
0.002369
0.000115














100
90
80
70
60

%E 50
40
30
20




-10


La Ce Pr Nd


Eu Gd Tb


Dy Er Tm Yb


Lanthanides
Figure A-22 Extraction plot for 1x10-3 M 2-15 in 1-Octanol with 3x10-3 M CO SAN with 1x10-4
M Lanthanides in 1 M HNO3.


Table A-22 Extraction data for Figure A-22.


E%
Error
0.1
0.2
0.3
1.1
0.4
0.2
0.6
1.0
0.2
0.5
0.7


D
-0.03835
-0.01297
-0.00571
-0.02437
0.000818
-0.00078
-0.00613
0.01419
0.004164
-0.00373
-0.00826


E %
-4
-1
-1
-2
0
0
-1
1
0
0
-1


6
0.0002
0.000361
0.000666
0.002291
0.000794
0.0005
0.0012
0.001973
0.000493
0.000896
0.001222














100
90
80
70
60
%E
50
40
30
20

10

La Ce Pr Nd Eu Gd Tb Dy Er Tm Yb

Lanthanides
Figure A-23 Extraction plot for 1x10-3 M 2-15 in CH2 12 with 3x10-3 M COSAN with 1x10-4 M
Lanthanides in 1 M HNO3.






Table A-23 Extraction data for Figure A-23.
E%
D E % Error 6
La 99.75926 99 0.2 0.000436
Ce 119.8254 99 0.1 0.000263
Pr 87.35385 99 0.2 0.000416
Nd 108.6396 99 0.2 0.000404
Eu 96.07937 99 0.6 0.001211
Gd 106.9662 99 0.2 0.000519
Tb 98.2 99 0.4 0.000907
Dy 134.0 99 0.2 0.000346
Er 63.30933 98 0.3 0.00066
Tm 90.36752 99 0.4 0.000785
Yb 91.83019 99 0.4 0.000643















100
90
80
70
60
%E
50
40
30
20

10

La Ce Pr Nd Eu Gd Tb Dy Er Tm Yb
Lanthanides

Figure A-24 Extraction plot for the second extraction for 1x10-3 M 2-15 in CH2 12 with 3x10-3 M
COSAN with 1x10-4 M Lanthanides in 1 M HNO3.




Table A-24 Extraction data for Figure A-24.
E%
D E % Error 6

La 2719.5 100 0.3 0.000473
Ce 258.5 100 0.7 0.001286
Pr 3827.667 100 0.3 0.000495
Nd 4055.667 100 0.0 7.07E-05
Eu 138.0 99 0.5 0.001106
Gd 356.389 100 0.1 0.000183
Tb 123.0 99 0.3 0.000693
Dy 606.5 100 0.1 0.000252
Er 46.10156 98 0.4 0.000902
Tm 2671.5 100 0.0 5.77E-05
Yb 377.4615 100 0.2 0.000289














100
90
80
70
60
%E
50
40
30
20

10

La Ce Pr Nd Eu Gd Tb Dy Er Tm Yb
Lanthanides

Figure A-25 Extraction plot for the third extraction for 1x10-3 M 2-15 in CH2 12 with 3x10-3 M
COSAN with 1x10-4 M Lanthanides in 1 M HNO3.





Table A-25 Extraction data for Figure A-25.
E%
D E % Error 6
La -132.123 101 0.2 0.000419
Ce -112.464 101 0.3 0.000568
Pr -3863.67 100 0.1 0.000265
Nd -104.612 101 0.1 0.000275
Eu -123.909 101 0.1 0.000252
Gd -98.3939 101 0.1 0.000231
Tb -99.5152 101 0.1 0.000183
Dy 1036.75 100 0.8 0.001738
Er -91.9158 101 0.2 0.000492
Tm -126.378 101 0.7 0.001288
Yb -70.47 101 0.2 0.000346














97
87
77
67
57
%E
47
37






La Ce Pr Nd Eu Gd Tb Dy Er Tm Yb

Lanthanides

Figure A-26 Extraction plot for 1x10-4 M 2-15 in 1, 2-dichloroethane with 1x10-3 M COSAN
with 1x10-4 M Lanthanides in 1 M HNO3.


Table A-26 Extraction data for Figure A-26.


E%
Error


E %
17
22
22
22
27
19
25
21
17
16
14


0.19983
0.284212
0.286093
0.281746
0.372033
0.23581
0.334997
0.258432
0.204249
0.191526
0.156468


0.001686
0.0006
0.002261
0.001229
0.002468
0.002402
0.004251
0.001159
0.001721
0.003027
0.005559






























II~LLII-I~I


Extraction Data for 2-16:


100
90
80
70
60
%E
50
40
30
20
10
0


La Ce Pr Nd Eu Gd Tb Dy


Er Tm Yb


Lanthanides

Figure A-27 Extraction plot for 1x10-3 M 2-16 in CH2 12 with 1x10-4 M Lanthanides in 1 M
HNO3 .



Table A-27 Extraction data for Finure A-27.


E%
Error


D
0.031845
0.03446
0.030968
0.027285
0.025866
0.03725
0.019533
0.006009
0.021154
0.031302
0.015307


E %


0.000513
0.000513
0.001739
0.001168
0.001442
0.000557
0.0002
0.000321
0.0003
0.002386
0.000416





























1111+~~31r3


100
90
80
70
60

%E 50
40
30
20
10


-10


Ce Pr Nd Eu Gd Tb Dy Er Tm


La


Lanthanides

Figure A-28 Extraction plot for 1x10-4 M 2-16 in 1, 2-dichloroethane with 1x10-3 M CO SAN
with 1x10-4 M Lanthanides in 1 M HNO3.




Table A-28 Extraction data for Figure A-28.


E%
Error


E %
5
7
5
6
6
4
3
2
4
0
2


0.055015
0.072324
0.049352
0.066007
0.059754
0.038412
0.032985
0.023125
0.042078
0.000899
0.021613


0.000513
0.000361
0.001097
0.000529
0.004631
0.002859
0.001401
0.001015
0.001907
0.002194
0.001212















97
87
77
67
57
%E
47
37
27
17
7
-3


La Ce Pr Nd Eu Gd Tb Dy Er Tm Yb
Lanthanides


Figure A-29 Extraction plot for the second extraction for 1x10-4 M 2-16 in 1, 2-dichloroethane
with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3.


Table A-29 Extraction data for Figure A-29.


E%
Error
0.8
0.6
0.8
0.5
0.3
0.7
1.1
0.4
0.4
0.2
0.5


D
0.006067
0.060697
0.042032
0.03613
0.029659
0.028494
0.016024
-0.00797
-0.01718
-0.00108
-0.0158


E %
1
6
4
3
3
3
2
-1
-2
0
-2


6
0.001411
0.001201
0.001604
0.000971
0.000513
0.001434
0.002428
0.000896
0.000833
0.0004
0.000913










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BIOGRAPHICAL SKETCH

Ozge Ozbek was born on November 26, 1976, in Izmir, Turkey. She started her

undergraduate studies in Chemistry in 1996 in Advanced Program (Honor Group) at Middle East

Technical University, in Ankara, Turkey. She continued her undergraduate studies in Advanced

Program until she received her Bachelors Degree in chemistry. During her undergraduate years,

she did undergraduate research studies on the synthesis and electronic spectroscopy of binuclear

rhodium complexes under the supervision of Dr. Huiseyin ISgi. She received her Bachelors

Degree in chemistry in June, 2000. Three months after her graduation, she started her studies for

Master of Science in chemistry. At the same time she became teaching assistant at the Chemistry

Department at Middle East Technical University. During her graduate years, she worked on

electrochemical and spectroscopic properties of binuclear platinum complexes under the

supervision of Dr. Hiiseyin ISgi and co-supervision of Dr. Ahmet M. Ojnal. In July 2002, she

received her Masters' Degree in chemistry. She came to University of Florida in August 2002

and started her studies for Doctor in Philosophy Degree (Ph.D.) in the Chemistry Department in

Inorganic Division under the supervision of Dr. Michael J. Scott. During her Ph.D. studies, she

worked on both computational and experimental projects. She performed computational

calculations on expanded porphyrin systems and worked on the synthesis of ligands for the

nuclear waste reprocessing studies. She received her Ph.D. in December, 2007.





PAGE 1

1 C3-SYMMETRIC NONADENTATE LIGAND SYS TEMS BEARING BOTH PYRIDINE AND DIAMIDE MOIETIES FOR THE EXTRAC TION OF LANTHANIDES AND ACTINIDES AND DFT LEVEL COMPUTATIONAL STUDIES FOR THE MOLECULAR ORBITALS AND ELECTRONIC TRANSITIONS OF EXP ANDED PORPHYRIN SYSTEMS BEARING BIS(NAPHTOAZULENEONE) RING SYSTEMS By OZGE OZBEK A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLOR IDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA 2007

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2 2007 Ozge Ozbek

PAGE 3

3 To my mom and dad

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4 ACKNOWLEDGMENTS First I would like to express my thanks to my research advisor Dr. Michael. J. Scott for valuable discussion and mentoring in chemistry. His enthusiasm for chemistry and his guidance made this study a successful one. I did learn a lot of chemistry during my studies and I am thankful for this to Dr. Scott. I also want to express my appreciation for him for being a responsible advisor and taking the full responsibi lity of his job. Today I am receiving my degree because he takes his responsibilities seriously. That is something I am going to appreciate for the rest of my life. I would have never made it to this point wit hout Dr. Adrian E. Roitb erg. I have a lot of things to thank him for. First of all he helped me to make my dream come true. He taught me computational chemistry starting from beginners le vel with a great patience. The more I wanted to learn, the more he taught me. Moreover he always supported me and encouraged me to go on my way and most importantly he always appr eciated and respected the work I was doing. In addition to his support for my research studies, he also supported me psychologically. Actually both Dr. Valeria D. Kleiman and Dr Roitberg supported and helped me a lot so that I made them my Argentinean parents here. I will always apprecia te their help and believing in me for the rest of my life. The most importan t and the most appreciable thi ng about Dr. Roitberg helping me with my computational studies is that he himself volunteered to help me. It was very nice of him and I want to thank him for doing this favor for me. I want to express my thanks to Dr. Daniel R. Talham and Dr. David E. Richardson for their endless support and their help for me. Their he lp, support and encouragement mean a lot to me and I will never forget it. One of the most important moments for me was the first moment I came to the Chemistry Department. It was Dr. James A. Deyrups very nice, friendly and warm welcome which made it

PAGE 5

5 so special and unforgettable. He also helped me a lot for a lot of things unt il he got retired. I am very much thankful to him for everything. I am also grateful to Dr. Ben W. Smith. When ever I needed him he was always there to help me and to support me. I appreciate him for a ll his help, support and his great understanding. One of the people who helped me a lot is Lori Clark. She has always been a great life saver and a great friend. She actually became my Am erican Mom and took really good care of me. I appreciate her help, suppor t and friendship a lot. Here in UF I have met extremely nice people and had the honor of getting friends with them. All of them are very special for me, deeply in my heart. Actually I prefer to call them as family rather than friends. We, altogether, shar ed a lot together. We shared our happiness, our unhappiness, good times, bad times and each moment ma de us come closer to each other and at the end we became a huge family. I want to tha nk all of them for sharing their good heart with me. I want to start thanking from Sarah M. La ne. She is my very first friend and my very appreciable support. She has done a ll the nicest things ever possibl e for me for five years. She has a very big heart, which I call diamond heart, and I am so happy to have her as my friend. Another very close friend with a lot of love, help and support with a big heart is Laurel Reitfort. Her enthusiasm of life has always cheered me up here. They both showed great hospitality with very warm feelings. There is a very sweet coupl e that I want to thank for becoming my family; Fedra Leonik and Daniel Kuroda. They are very thoughtful, caring, helpful, nice, and full of love. They both do have a very big heart to share. I am grateful to them for all the nice things they have done for me. Another member of my huge family is Melanie Veige. I will always remember her with the colorful flowers that sh e gave me from her garden. She is super nice, thoughtful, helpful and supportive. I am so glad to be friends with such a person with nothing but

PAGE 6

6 goodness in her heart. Also it was a great pleasure for me to discuss chemistry with her as well. There is another couple that I enjoy sharing a tr ue family relation: Dr. Ranjan Mitra and Rashmi Bagai. They are definitely a family for me. Ranjan is like a protecting brot her to me. He has been patient enough to answer all the que stions I ask and he taught me a lot of stuff in the lab. He was always helpful and full of support and a great brothe r. Rashmi has always been like a sister to me with her kind, thoughtful, warm loving heart. I sh ared a lot with her and am glad to have both Ranjan and her in my life as a family. Another big support for me is Sinan Seluk. He is super nice, friendly and full of support. I do not thi nk I could have survived here without him. I also thank to Scott Group members. It was a pleasure to work with Dr. Ivana Bozideravic and Dr. Hubert Gill. We had great discussions with Dr. Gill on porphyrin systems. I also want to thank Dr. Elon Ison for all his help for the comput ational studies. He was a great person, a great friend and a big support. Also I am grateful to Dr. Ajah Sah and Dr. Priya Srinivasan for their help and friendships. I also want to thank Cand ace Zieleniuk and Eric Libra for being very nice lab mates for four years. I appreciate all their help. Many thanks need to go all the way to Turk ey as well. I want to thank to the two professors I worked years ago who have been su pporting me with their emails. I am grateful to Dr. Hseyin I i and Dr. Ahmet M. nal. They always be lieved in me and they always told me to go on. I will always appreciate their suppor t and cheering me up with their emails. Lastly and most importantly I want to thank to the most precious people in my heart; my mom Betl zbek, and my dad, Nihat zbek. They make my life a fairy tale. I couldnt have wished for a better family. I consider myself th e luckiest person in the world to have such a family. There is nothing important as much as my family. No matter how tough life is, as long as I feel their love I feel I can do anything in life. I do not know how to thank them for being such a

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7 family to me. Even if I bought all the flowers and all the gifts for them, it wouldnt be enough how much I am thankful to them and how much I love them. I have one last thing to say to my parents: I love you, mom and I love you, dad and nothing else matters. Chairmans Comments Inorganic chemistry is a very la rge field to work in. It has a lot of applications in industry as well as in academic research. The field of i norganic chemistry is clos ely related to physical chemistry, organic chemistry, biochemistry and i ndustrial chemistry. The reason it is related to these other fields of application of chemistry is that the main interests of inorganic chemists are the transition metals, reaction kinetics, spectrosc opy and the molecular or bital approach to be able to understand experimental results from th e point of theory. A lot of biological reactions take place in a cell and transition metals and thei r complexes are involved in these reactions as biological catalysts. Moreover a lo t of transition metals are used for pharmacologic research to develop new medicines. The most famous of this application is the cis platinum complex that is being used for cancer drugs and its derivatives are under study by bioinorganic chemists to further develop more effective medicine for cancer. On the other hand there is a big contribution of inorganic chemistry to the industry. A lot of processes that involve chemical reactions in industry need transition metals and their complexes for the catalysis of th ese reactions to occur in the fa stest way, and the most economic way. That is why a lot of catalys is research is going on to deve lop new catalysts for industrial purposes. Another interest of inorganic chemistry is the spectroscopy. Appr oaching spectroscopy with respect to theory is of great interest. Transi tion metals or some of the ligands that transition metals make complexes with show very intere sting spectroscopic propert ies. Therefore their spectroscopic behaviors are extensively studied and the reason of the transitions taking place in

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8 the spectra of these molecules is explained w ith the molecular orbital approach which is commonly used in inorganic chemistry to provide an explan ation theoretically. As a result of being in a wide area of a re search field, we were interested in both the industrial application of inorganic chemistry and th e spectroscopic studies. Our research from the side of industrial ap plication of inorganic chemistry was to do research to develop a new, efficient ligand system to react with lanthanide and actinide cations selectively to be able to separa te them from each other. This is a very important task because every day in nuclear reactors a lo t of radioactive waste is genera ted. These wastes are extremely harmful for the environment and the human health but unfortunately it can not be converted into a short term waste or less harmful waste since the process to achieve this goal goes through the selective separation of these chemically very similar metal ions from each other. A lot of research around the world is being done to solv e this problem. Theref ore we prepared a new ligand system and tried to see if it is going to be efficient for the industrial application. The half of this document involves the research on these ligand systems for the nuclear waste management. We were also interested in the spectroscopi c properties of the porphyrin systems. These systems are biologically important systems esp ecially with their presence in hemoglobin. In addition to important biological activities of these molecules, they show every interesting spectroscopic propertie s. Wide research has been going on wi th the spectroscopic properties of these molecules. Gouterman developed a th eoretical explanation for the spectroscopic characteristics of these molecules from mo lecular orbital appro ach. Although a lot of spectroscopic research has been done with the s imple porphyrin systems, there is not too many with large porphyrin systems. In order to see how the substituents affect the spectroscopic

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9 properties of these molecules, in our lab larg e porphyrin molecules called Azuleneones were synthesized and experimental st udies for the electronic spectroscopy of these molecules were performed. In order to be able to understand the interesting spectroscopic behaviors of these molecules we focused on working on these molecule s from theoretical approach and be able to explain the electronic transitions taking place with respect to theory. Th e second half of this work is the detailed study of the theoreti cal studies of these porphyrin derivatives. In conclusion, this document combines more than one application of inorganic chemistry in detail: industrial and theore tical application. Deta ils of the results are presented herein.

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10 TABLE OF CONTENTS page ACKNOWLEDGMENTS...............................................................................................................4 CHAIRMANS COMMENTS........................................................................................................7 LIST OF TABLES................................................................................................................. ........13 LIST OF FIGURES................................................................................................................ .......15 LIST OF SCHEMES................................................................................................................ ......19 ABSTRACT....................................................................................................................... ............20 CHAPTER 1 INTRODUCTION..................................................................................................................22 1.1 Nuclear Waste............................................................................................................. ..22 1.2 Nuclear Incineration of TransUranium Actinides: Transmutation..............................23 1.3 Chemical Properties of Lanthanides and Actinides......................................................23 1.4 Solvent Extraction Processes for the Nuclear Waste Treatment...................................24 1.4.1 Extraction Processes with Extrac tants Containing Phosphorus Atoms............26 1.4.1.1 PUREX process..................................................................................26 1.4.1.2 TRUEX process..................................................................................26 1.4.1.3 TRPO process.....................................................................................27 1.4.1.4 DIDPA process...................................................................................27 1.4.1.5 UNEX process....................................................................................28 1.4.2 Extraction Processes with Incinerable Extractants...........................................28 1.4.2.1 DIAMEX process...............................................................................28 1.4.2.2 SANEX process..................................................................................30 1.4.3 Pre-organized Ligand Systems for Nuclear Waste Processing.........................31 1.4.3.1 Calixarenes.........................................................................................32 1.4.3.2 Cavitands............................................................................................32 1.4.3.3 Tripodands..........................................................................................33 1.4.3.4 Trityls..................................................................................................33 1.5 The Research Objectives...............................................................................................35 2 NEW NONADENTATE LIGANDS AS CANDIDATES FOR ACTINIDE/LANTHANIDE SEPARATION: PYRIDINE-2, 6-DICARBOXAMIDE DERIVATIVES OF THE TRIPHEN OXYMETHANE PLATFORM BEARING PYRIDINE-DIAMIDE MOEITIES.......................................................................................43 2.1 Ligand Design............................................................................................................. ..43 2.1.1 Recently Reported Extraction Studies with Pyridine-2, 6-dicarboxamides......45 2.1.2 Research Objectives..........................................................................................46

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11 2.2 Synthesis of the Nonadentate Ligand Systems.............................................................47 2.2.1 Synthesis of Triphenoxymethane Platforms with Amine Groups.....................47 2.2.2 Synthesis of 6-(N, N-dialkylca rbamoyl)pyridine-2-carboxylic Acid...............48 2.2.3 Synthesis of the Ligands...................................................................................49 2.3 Conclusion................................................................................................................ ....50 2.4 xperimental Section.......................................................................................................50 2.4.1 General Considerations.....................................................................................50 2.4.2 Synthesis...........................................................................................................51 3 EXTRACTION EFFICIENCIES OF C3-SYMMETRIC NONADENTATE LIGAND SYSTEMS WITH LANTHANIDE (III) CATIONS IN ACIDIC MEDIUM........................65 3.1 Introduction.............................................................................................................. .....65 3.2 Results and Discussion..................................................................................................66 3.2.1 Extraction Experiments.....................................................................................66 3.2.2.1 Extraction Pproperties of th e ligands with the upper side functionalized triphenoxymethane platform.......................................67 3.2.2.2 Extraction properties of the ligands with the lower side functionalized triphenoxymethane platform.......................................68 3.2.2.3 Following the extraction efficiency of 2-13 by NMR spectroscopy.......................................................................................71 3.2.3 Solid State Structures of 2-10, 2-13, and [2-10 M]3+, (M=Tm, Yb).................72 3.3 The Factors Affecting th e Extraction Performance of Nonadentate Pyridine-2, 6dicarboxamide System..................................................................................................76 3.3 Conclusion................................................................................................................ ....80 3.4 General Procedure for the Pr eparation of [2-10Ln] [Ln(NO3)5] [NO3] (Ln=Tm, Yb)............................................................................................................................ ....81 3.5 X-ray Crystallography...................................................................................................81 4 INTRODUCTION..................................................................................................................85 4.1 Porphyrins................................................................................................................ .....85 4.2 Goutermans Four Orbital Model for th e Spectroscopic Properties of Porphyrins......85 4.3 Theory and Computational Chemistry..........................................................................88 4.3.1 General aspects of Quantum Chemistry............................................................88 4.3.2 Basis Sets..........................................................................................................91 4.3.3 Density Functional Theory................................................................................93 4.3.3.1 Hohenberg-Kohn theorems.................................................................93 4.3.3.2 Kohn-Sham equations.........................................................................94 4.3.4 Electronic Spectroscopy....................................................................................96 5 COMPUTATIONAL CALCULATIONS FOR CIS -AZULENEONE AND TRANS AZULENEONE....................................................................................................................101 5.1 Computational Approach to Po rphyrins and Porphyrin Derivatives..........................101 5.2 Computational Methods..............................................................................................102

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12 6 MOLECULAR ORBITAL APPROACH FOR THE ELECTRONIC EXCITED STATES OF CIS -AND TRANS -AZULENEONE................................................................105 6.1 Molecular Structures...................................................................................................105 6.2 Calculated Orbitals and the Spectra for the cis and trans Derivatives of Azuleneone..................................................................................................................106 6.2.1 Kohn-Sham Orbitals.......................................................................................108 6.2.2 Excited States..................................................................................................112 6.2.2.1 Q-band regions for cisAzuleneone and transAzuleneone..............112 6.2.2.2 B-band regions for cis -Azuleneone and trans -Azuleneone..............116 6.2.2.3 Oscillator strengths...........................................................................118 6.3 Conclusion................................................................................................................ ..119 7 SUMMARY........................................................................................................................ ..126 APPENDIX: EXTRACTION DATA..........................................................................................128 LIST OF REFERENCES.............................................................................................................157 BIOGRAPHICAL SKETCH.......................................................................................................166

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13 LIST OF TABLES Table page 3-1 X-ray data for the crystal structures 2-10, 2-13, and the metal complexes of 2-10 with Tm and Yb.................................................................................................................74 3-2 Selected bond lengths () for the 2-10, 2-13, and metal complexes of 2-10 with Tm and Yb......................................................................................................................... .......77 6-1 Selected experimental and calculated a ngles on the porphyrin core for 5-1a and 5-1b .106 6-2 Calculated Molecular Orbitals, Sy mmetries and Energies (eV) for 5-1b and 5-2b ........109 6-3 Calculated electronic excite d states, orbital configurationsa, b (% Weight), transition energies and oscillator strengths for th e first fifteen singlet states for 5-1b and 5-2b.....113 A-1 Extraction data for Figure A-1.........................................................................................128 A-2 Extraction fata for Figure A-2..........................................................................................129 A-3 Extraction data for Figure A-3.........................................................................................130 A-4 Extraction data for Figure A-4.........................................................................................131 A-5 Extraction data for Figure A-5.........................................................................................132 A-6 Extraction data for Figure A-6.........................................................................................133 A-7 Extraction Data for Figure A-7........................................................................................134 A-8 Extraction data for Figure A-8.........................................................................................135 A-9 Extraction data for Figure A-9.........................................................................................136 A-10 Extraction data for Figure A-10.......................................................................................137 A-11 Extraction data for Figure A-11.......................................................................................138 A-12 Extraction data for Figure A-12.......................................................................................139 A-13 Extraction data for Figure A-13.......................................................................................140 A-14 Extraction data for Figure A-14.......................................................................................141 A-15 Extraction data for Figure A-15.......................................................................................142 A-16 Extraction data for Figure A-16.......................................................................................143

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14 A-21 Extraction data for Figure A-21.......................................................................................148 A-22 Extraction data for Figure A-22.......................................................................................149 A-24 Extraction data for Figure A-24.......................................................................................151 A-25 Extraction data for Figure A-25.......................................................................................152 A-26 Extraction data for Figure A-26.......................................................................................153 A-27 Extraction data for Figure A-27.......................................................................................154 A-28 Extraction data for Figure A-28.......................................................................................155 A-29 Extraction data for Figure A-29.......................................................................................156

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15 LIST OF FIGURES Figure page 1-1 Schematic representation of a tr icapped trigonal prismatic geometry...............................37 1-2 Schematic structure of chloro-COSAN ion.......................................................................37 1-3 Selected phosphorus containing extractants......................................................................38 1-4 Selected diamide extractants..............................................................................................39 1-5 Selected pyridine bearing heterocyclic extractants............................................................40 1-8 Trityl ligand systems...................................................................................................... ....42 2-1 Structures of a N, N, N, N-tetraethy lpyridine-2, 6-dicarbox amide and its tripodal derivatives with b TREN and c. Me-TRPN........................................................................60 2-2 Structures of some r ecently studied DPA ligands..............................................................61 3-1 NMR scale extraction data with 2-13................................................................................82 3-2 Crystal structure of 2-10.................................................................................................. ..83 3-3 Crystal structures of [2-10 M]3+, M= Tm, Yb...................................................................83 3-4 Crystal structure of 2-13.................................................................................................. ..84 4-1 Structure of porphyrin..................................................................................................... ...99 4-2 Goutermans four orbital model for a D4h porphyrin.........................................................99 4-3 Possible transitions among the four orbi tals of the porphyrins with the change of ordering of the orbitals.....................................................................................................100 4-4 The transitions for absorption and emi ssion between the ground and excited states..... .100 5-1 Schematic representation of a cis Azuleneone, 5-1a, and its simplified derivative 5.1b created for the calculations b transAzuleneone, 5-2a 5and its simplified derivative 5-2b used in the calculations...........................................................................104 6-1 Crystal structure of 5-1a.................................................................................................. .119 6-2 Experimental bond lengths for 5-1a.................................................................................120 6-3 Calculated bond lengths for 5-1b ....................................................................................120 6-4 Calculated bond lengths for 5-2b.....................................................................................121

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16 6-5 Numbering scheme for the cis isomer for the selected atoms.........................................121 6-6 Experimental and calculated electronic spectra for 5-1b.................................................122 6-7 Experimental and calculated electronic spectra for 5-2b.................................................122 6-8 Kohn Sham orbital energy diagrams for so me of the frontier orbitals of 5-1b and 52b, respectively............................................................................................................... .123 6-9 Isoamplitude surfaces of the wave func tions of 5-1b and 5-2b for some of their frontier orbitals, respectively...........................................................................................124 6-10 Gaussian broadening curve and th e actual Uv-Vis spectrum for the cis isomer.............125 6-11 Gaussian broadening curve and th e actual Uv-Vis spectrum for the trans isomer..........125 A-1 Extraction plot for 1x10-3 M 2-10 in CH2Cl2 with 1x10-4 M Lanthanides in 1 M HNO3............................................................................................................................... .128 A-2 Extraction plot for the second extraction for1x10-3 M 2-10 in CH2Cl2 with 1x10-4 M Lanthanides in 1 M HNO3...............................................................................................129 A-3 Extraction plot for the third extr action for 1x10-3 M 2-10 in CH2Cl2 with 1x10-4 M Lanthanides in 1 M HNO3...............................................................................................130 A-4 Extraction plot for 7.63x10-3 M 2-10 in CH2Cl2 with 1x10-4 M Lanthanides in 1 M HNO3............................................................................................................................... .131 A-5 Extraction plot for 1x10-3 M 2-10 in 1-Octanol with 1x10-4 M Lanthanides in 1 M HNO3............................................................................................................................... .132 A-6 Extraction plot for 1x10-2 M 2-10 in 1, 2-dichloroethane with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3................................................................................133 A-7 Extraction plot for 1x10-3 M 2-11 in CH2Cl2 with 1x10-4 M Lanthanides in 1 M HNO3............................................................................................................................... .134 A-8 Extraction plot for 1x10-3 M 2-12 in CH2Cl2 with 1x10-4 M Lanthanides in 1 M HNO3............................................................................................................................... .135 A-9 Extraction plot for the second extraction for 1x10-3 M 2-12 in CH2Cl2 with 1x10-4 M Lanthanides in 1 M HNO3...............................................................................................136 A-10 Extraction plot for 1x10-3 M 2-13 in CH2Cl2 with 1x10-4 M Lanthanides in 1 M HNO3............................................................................................................................... .137 A-11 Extraction plot for the second extraction for 1x10-3 M 2-13 in CH2Cl2 with 1x10-4 M Lanthanides in 1 M HNO3...............................................................................................138

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17 A-12 Extraction plot for the third extr action for 1x10-3 M 2-13 in CH2Cl2 with 1x10-4 M Lanthanides in 1 M HNO3...............................................................................................139 A-13 Extraction plot for 1x10-4 M 2-13 in 1, 2-dichloroethane with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3................................................................................140 A-14 Extraction plot for the second extraction for 1x10-4 M 2-13 in 1, 2-dichloroethane with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3.................................141 A-15 Extraction plot for the third extr action for 1x10-4 M 2-13 in 1, 2-dichloroethane with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3.........................................142 A-16 Extraction plot for 1x10-3 M 2-13 in 1, 2-dichloroethane with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3................................................................................143 A-17 Extraction plot for the second extraction for 1x10-3 M 2-13 in 1, 2-dichloroethane with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3.................................144 A-18 Extraction plot for 1x10-3 M 2-14 in 1, 2-dichloroethane with 3x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3................................................................................145 A-19 Extraction plot for 1x10-3 M 2-15 in 1-Octanol with 1x10-4 M Lanthanides in 1 M HNO3............................................................................................................................... .146 A-20 Extraction plot for the second extraction for 1x10-3 M 2-15 in 1-Octanol with 1x10-4 M Lanthanides in 1 M HNO3...........................................................................................147 A-21 Extraction plot for the third extr action for 1x10-3 M 2-15 in 1-Octanol with 1x10-4 M Lanthanides in 1 M HNO3...............................................................................................148 A-22 Extraction plot for 1x10-3 M 2-15 in 1-Octanol with 3x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3...........................................................................................149 A-23 Extraction plot for 1x10-3 M 2-15 in CH2Cl2 with 3x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3...............................................................................................150 A-24 Extraction plot for the second extraction for 1x10-3 M 2-15 in CH2Cl2 with 3x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3.........................................................151 A-25 Extraction plot for the third extr action for 1x10-3 M 2-15 in CH2Cl2 with 3x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3.........................................................151 A-26 Extraction plot for 1x10-4 M 2-15 in 1, 2-dichloroethane with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3................................................................................153 A-27 Extraction plot for 1x10-3 M 2-16 in CH2Cl2 with 1x10-4 M Lanthanides in 1 M HNO3............................................................................................................................... .154

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18 A-28 Extraction plot for 1x10-4 M 2-16 in 1, 2-dichloroethane with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3.......................................................................155 A-29 Extraction plot for the second extraction for 1x10-4 M 2-16 in 1, 2-dichloroethane with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3.................................156

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19 LIST OF SCHEMES Scheme page 2-1 Reaction scheme for the synt hesis of 2-6, 2-7, 2-8 and 2-9..............................................62 2-2 Synthetic scheme for 2-5...................................................................................................62 2-3 Synthesis of 2-10 and 2-11................................................................................................63 2-4 Synthetic scheme for 2-12.................................................................................................63 2-5 Synthesis of 2-13 and 2-15................................................................................................64 2-6 Synthesis of 2-14 and 2-16................................................................................................64

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20 Abstract of Dissertation Pres ented to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy C3-SYMMETRIC NONADENTATE LIGAND SYS TEMS BEARING BOTH PYRIDINE AND DIAMIDE MOIETIES FOR THE EXTRAC TION OF LANTHANIDES AND ACTINIDES AND DFT LEVEL COMPUTATIONAL STUDIES FOR THE MOLECULAR ORBITALS AND ELECTRONIC TRANSITIONS OF EXP ANDED PORPHYRIN SYSTEMS BEARING BIS(NAPHTOAZULENEONE) RING SYSTEMS By Ozge Ozbek December 2007 Chair: Michael J. Scott Major: Chemistry Separation of radioactive actinides from lantha nides in nuclear wast e is important since transmutation of actinides in the presence of la nthanides is impossible. Nonadente ligands were synthesized with the introduction of unsymmetri cal pyridine-2, 6-dicarboxamide groups to the preorganizing triphenoxymethane platform. Th e new incenerable ligand systems have the advantage of combining both the pyridine a nd diamide groups on one platform to work cooperatively for the extraction of trivalent meta ls from acid solutions. Ligand systems with two different types of triphenoxyme thane platforms, lower side functionalized tr iphenoxymethane platform and upper side functionalized triphenoxym ethane platform, have been synthesized. The results of the extraction experiments with trivalent lanthanides in 1 M nitric acid solutions reveal that all the ligand systems show moderate extrac tion of lanthanides by themselves but when the synergist COSAN is used, enhanced extracti on behaviors are observed with lower side functionalized ligands except with the ligand with octyl protected platform with isopropyl groups as substituents. The results indicate that the solubility of the comp lexes forming during the extractions and the relative concentrations of th e synergist COSAN, the extraction ligand and the

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21 metal play major role for the extraction behaviours of the ligands. Also, solid state structures of the complexes with upper side f unctionalized ligand with Tm a nd Yb indicate the geometry around metal is tricapped trigonal prism as expect ed for the metal complex with lanthanide (III) ions. The synthesis of the ligan ds and the results of the extr action experiments are discussed herein. The efficiencies of the ligands are compared. The electronic properties of the expanded porphyrin systems, cis and trans -azuleneone derivatives, were of interest and computational studies of these molecules have been performed at DFT level. Excited state calculations were performed with TDDFT. The calculated and experimental geometries for the cis isomer were compared and the results were determined to be in good agreement. Calculated excited states for e ach of the molecules were also consistent with the experimental spectra of the molecules. Detailed analysis of the calculated orbitals, orbital energies and both the experimental and the calculat ed spectra of the molecules revealed that the cisisomer has split Q band region due to electro nic affects of the substituents and symmetry lowering. Also the B-band regions of both of the molecules show contributions coming from lower lying orbitals. Both the experimental a nd theoretical results reveal that both of the molecules are red shifted due to conjugation. All the de tails of the analysis and comparisons of the calculated and experiment al data are discussed herein.

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22 CHAPTER 1 INTRODUCTION 1.1 Nuclear Waste Radioactive materials are used for diffe rent purposes and among them production of energy is the most important one By using nuclear energy, electr icity is produced at nuclear power plants.1 Today, the electricity gene rated with nuclear power provides 15 % of the total electricity generated around the world.2 The demand for energy is increasing more and more every day with the development of technol ogy. Search for economic and environmentally friendly source of energy to replace fuel energy is underway. In this aspect, nuclear energy is a good candidate for future energy production. Nuclear energy production has one major problem to be solved. The use of radioactive materials causes the generation of nuclear wa ste. As a result, the contamination of the environment by radioactive materials and their nega tive impacts on the health of individuals is a growing public concern.3 Actinides (An), present in nuclear waste, are some of the most dangerous radioactive elements because they have long half-lives and activity. The half lives of the actinides range between a few hundred years and a few thousand years or more.4 Even small amounts of these nuclides can cause severe health hazards.3 During the decay of unstable nuclei, or rays are emitted with very high energy which can cause biological damage resulting in cancer5 or genetic disorders.5, 6 Due to the potential dangers of actinides in nuclear waste, waste reprocessing is essential to provide both human and environmental safety. For the reprocessing of the waste, research has been done for the separation of lanthanide (III) io ns from chemically similar actinide (III) ions. There are three major ways to manage nuclear waste: recycling of the actinides, direct geological disposal of the waste a nd long term monitoring of the waste.7 Currently, actinide

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23 recycling and short term mon itoring are the most common appr oaches used. The lifetime of natural and engineered barriers proposed for long term storage is under question. Therefore it possesses a safety threat.7 1.2 Nuclear Incineration of TransUranium Actinides: Transmutation The primary goal of nuclear waste reprocessing is transmutation which is the conversion of long-lived minor actinides (e.g. americium), into short-lived isotopes by neutron bombardment.8, 9 During this process, energy and neutrons are released in addition to fission products. The fission products remain radioactiv e but they decay in a shorter time than the parent molecule. The transmutation process is very important for long term nuclear waste management. The success of the transmutation pr ocess requires pure targets.10 Therefore separation of trivalent actinides from trivalent lanthanides is necessary ; otherwise the lanthanide s absorb neutrons and prevent neutron capture by th e transmutable actinides.11 1.3 Chemical Properties of Lanthanides and Actinides Although transmutation provides an efficient wa y of converting long-lived minor actinides into short-lived isotopes, it is generally not applicable because trivalent actinides and trivalent lanthanides coexist in most nuclear waste. Efficient separation of actinides and lanthanides is a challenge because actinide (III) cations heavier th an plutonium (Pu) are chemically similar to lanthanide (III) cations. The trivalent charge is commonly observed fo r most lanthanide and actinide ions except for the early (thorium and plutonium) actinides or the late actinide nobeli um because the actinide 5f orbitals have smaller spatial distribution and en ergy than the series and special distributions of 6d, 7s, and 7p orbitals.12 The spatial distribution of actinide 5f orbitals are greater compared to the 7s and 7p orbitals than the sp atial distribution of the lanthanide 4f orbitals with respect to the 6s and 6p orbitals. The larger spat ial distribution of actinide 5f orb itals makes them slightly more

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24 covalent than the lanthanides.13 In a study, it was reported for Am and Eu that, the sigma bond energy of Am is higher than that of Eu with su lfur which indicates that spatial extent of 5f orbitals play a crucial role for the covale ncy in spite of thei r higher orbital energy.14 Moreover the interaction of the metallic core with the surro unding ligands in coordination complexes of lanthanide (III) ions is mainly electrostatic be cause the 4f valence shells of the trivalent lanthanides are shielded from exte rnal perturbations by the filled 5s2 and 5p6 orbitals.15 The greater covalency of the trivalent actinides with respect to trivalent lanthanides is the only significant difference between these two f bl ock elements. Therefore ligands with softer donor atoms, such as N, S or Cl, relative to oxygen are suggeste d for the discrimination of actinides from lanthanides.12 Variable coordination numbers and geometries have been observed both for tripositive lanthanide and actinide ions. The observed coordi nation numbers for the lanthanide (III) ions range between 6 and 12.16, 17 Nine coordination is common fo r the lanthanide (III) ions and several complexes are reported having trica pped trigonal prismatic geometry with nine coordination sites.18, 19, 20 Nona aqua complexes of lanthanide (III) ions are in tricapped trigonal prism geometry. The tricapped trigonal prisma tic geometry is depicted in Figure 1-1. 1.4 Solvent Extraction Processes for the Nuclear Waste Treatment Safe disposal of nuclear wast e is a primary concern, and to this end, the development of separation techniques for tr ivalent actinides from trivalent lant hanides is essential for the nuclear waste reprocessing. Research studies have been focused on liquid-liquid extraction processes because it is the most successful technique. Du ring liquid-liquid extraction, the charged metal ion is extracted as a complex with an extract ant from a highly acidic aqueous phase into an immiscible organic phase.21 For effective separation the legends of the extract ant should have minimal solubility in the aqueous phase.22 The complication reaction oc curs in the interfacial

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25 zone between the organic and aqueous phases.22 The extent of extractability of the metal is measured by the distribution ratio (D), which is the ratio of concentration of the metal in the organic phase to its concentra tion in the aqueous phase. Also of importance is the separation factor (SF) which is the ratio of the distribution ratios of lantha nide and actinide ions, indicating the selectivity of the extractant.8 Lanthanide and actinide captions are transferred from the aqueous solution into the organic phase in tight complex formation. During this pr ocess, the metal is su rrounded by the uncharged ligands to form a charged complex. In addition to the complex, hydrated nitrate anions can be transferred to the organic phase with the metal cation.23 When cobalt bis(dicarbollid e) anion (1-), closo-[(1,2-C2B9H11)2-3,3-Co]-, COSAN, is used as a coextractant enhanced extract ion ratios are sometimes observed.24 The ion pair formation with the charged complex and the COSAN is due to the great hydrophobicity of the COSAN anion.24 This way hydration of the co mplex is lowered so that it becomes more soluble in the organic phase. The chemical stability of COSAN in nitric acid is enhanced by the halogenation of the most reactive terminal hydrogen atoms. COSAN derivatives are stable to radiation. In Figure 1-2 the structure of chloro -COSAN is depicted. Since COSA N derivatives are insoluble in hydrocarbons, moderately polar solvents, such as aromatic nitro compounds, halogenated ethers, etc., are used for the extractions.25 The first step of nuclear waste reprocessing is the dissolution of used fuel rods in nitric acid. Initially, several processes have been developed including the PUREX, TRUEX, TRPO, DIDPA, and UNEX processes. In PUREX pro cess industrial uranium and plutonium are recovered from the generated wast e. TRUEX process removes actinid es and lanthanides from the liquid waste that was generated during PUREX process. Although these processes are successful

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26 in terms of selectivity and high extraction effi ciencies of the extractions, they all involve phosphorus containing reagents which creates a secondary waste stream.26 As an alternative to TRUEX process and the other pr ocesses, incinerable proce sses containing only carbon, oxygen hydrogen and nitrogen atoms are being developed to minimize ge neration of secondary waste,27 and utilizing diamides, the DIAMEX pr ocess is among the most promising ones.27 Another approach to incinerable extraction systems is SANEX process. SANEX process employs pyridine, pyrazolone and other heterocyclic mol ecules as ligands to make the coordination site more covalent in nature and incr ease the selectivity for actinides.12, 26, 27 1.4.1 Extraction Processes with Extrac tants Containing Phosphorus Atoms 1.4.1.1 PUREX process The PUREX (Plutonium and Uranium Reduction Ex traction) process efficiently isolates U and Pu from the mixture of fission products.28 With a water immiscible organic phase such as tributylphosphate (TBP), the unwanted metal ions (fission products) are extr acted into the nitric acid medium and Pu (IV) and U (IV) move into the organic phase. 27 The structure of TBP is given in Figure 1-3. There are three purification cy cles. Although 99.9% of the fissi on products are separated in the first cycle, to increase the efficiency of th e separation the same pro cess is repeated in the second and third cycles.27 During the first cycle U (IV) and Pu (IV) are extracted with TBP, and then Pu (IV) is reduced to Pu (III). In this wa y Pu (III) and U (IV) are separated from each other with another extraction since Pu (III) is less ex tracted than U (IV) with TBP. The last step involves the uranium stripping from the TBP phase.27 1.4.1.2 TRUEX process The transuranic element extrac tion (TRUEX) process is a liqu id-liquid extraction process for the recovery of actinides from liquid waste.29 For this process octyl(phenyl)-N, N-

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27 diisobutylcarbamoylmethylphosphine oxide (CMPO) is used as an extractant with paraffin diluents.30 The structure of CMPO is shown in Figur e 1-3. TBP is also used as a solvent modifier as it enhances th e extraction of metal cations.29 Detailed research has been carried out for the distribution behavior of the TRUEX pr ocess for the actinides, lanthanides and some fission products29, 30 CMPO is a very powerful extractant. It is reported that greater than 99.99% of Am from the organic phase could be rem oved by using simulated waste solutions with CMPO.27 During the process, chelating CMPO binds the M3+ cation tightly by its C=O and P=O donor atoms. After the formation of the cation complex, polar nitrate ions are transferred together with the cation for charge compensation.31 1.4.1.3 TRPO process Actinides with (III), (IV) and (VI) oxidation states are extracted from nitric acid by trialkylphosphine oxide extracta nts (Cyanex 923). U (VI), Np (IV, VI) and Pu (VI) are extracted with 99% by using TRPO (with alkyl chains C6 to C8) in kerosene.27 The structure of TRPO can be seen in Figure 1-3. TRPO/TBP mixture in kero sene reportedly showed high extractability for UO2 2+.32 The TRPO process is advantageous due to th e low cost of the tr ialkylphosphine oxide reagents and high extraction efficiency for several actinide and lanthanide elements.27 However, the process has the disadvantage of being efficient at only dilute ni tric acid concentrations, which increases the amount of the liquid waste to be treated. 27 1.4.1.4 DIDPA process In this process diisodecylphosphor ic acid (DIDPA) is used as th e extractant. In Figure 1-3 the structure of DIDPA is given. U(VI), Pu(IV ), Np(IV), Am(III), Cm(III) and lanthanides (III) are successfully extracte d with a mixture of DIDPA and TBP at certain concentration. Numerous studies with dialkylphosphoric acids, of the di-2ethylhexy lphosphoric acid (D2EHPA) type,

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28 dialkyldithiophosphinic acid (C yanex 301) or their synergis tic mixtures with neutral phosphorous extractants have been done for th e extraction of Nd(III), U(VI), Th(IV), Am(III) etc., from nitric acid solutions a nd efficient extractions for trivalent actinide/lanthanide elements are achieved.27, 33, 34 The structure of Cyanex 301 is shown in Figure 1-3. The disadvantages of DIDPA process are sim ilar to those of TRPO. This process also requires high dilutions and denitration resulting in a greater volume of waste solution to be treated.27 1.4.1.5 UNEX process The universal extraction (UNEX) process us es a synergistic mixture containing the hexachloro derivative of cobalt dicarbollide (CCD), polyethylene glycol (PEG) and diphenylcarbamoylmethylphosphine oxide.4 Cs (I), Sr (II) and seve ral actinides and lanthanides are extracted. CCD extracts Cs (I), PEG ex tracts Sr (II) and the CMPO extracts the actinide/lanthanide metals.27 When the waste solution was diluted with HF to prevent huge extraction of Fe and Zr instead of Eu (III), pr omising results were obt ained. Several research studies are being done for the op timization of the UNEX process.27 1.4.2 Extraction Processes with Incinerable Extractants 1.4.2.1 DIAMEX process The DIAMEX (Diamide Extraction) process wa s developed for the selective co-extraction of trivalent actinides and trivalent fi ssion lanthanides from nuclear waste.35 The diamide extractants used for this process, such as mal onamides, succinamide, glutalamide and adipamide, are incinerable. These compounds are weak base s in which the carbonyl amide groups coordinate to metal ions in a chelate complex.36 They have strong complexation with the metal ion and are able to extract metal ion from highly acidic solutions.37 Either one or two malonamides are bound to the lanthanide ion and nitrate ions and/ or water molecules complete the coordination

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29 sphere of the metal.38 In crystal structures of Am3+ and Nd3+ with N, N, N, Ntetraethylmalonamide, TEMA, both of the metal ions have the same coordination geometry with two TEMA molecules coordinating through their carbonyl groups and the remaining coordination sphere is completed wi th three bidentate nitrate ions.39 The structure of TEMA is depicted in Figure 1-4. Among the malonamides used for the extr action purposes, N, N-dimethylN, Ndibutyltetradecylmalonic diamide (DMDBTDMA) was proposed as a promising extractant.35 Recent studies suggest that N, N-dihexyl octanamide ( DHOA), N, N-di(2-ethylhexyl) isobutyramide (D2EHIBA), and N, N-dimet hyl-N, N-dioctyl-hexylethoxy-malonamide (DMDOHEMA) are good extractants as well.40, 41 The structures of DMDBTDMA and D2EHIBA can be seen in Figure 1-4. N -dihexyl octanamide (DHOA) and N, N-di(2-ethylhexyl) isobutyramide (D2EHIBA) are proposed to be a promising alternative for TBP for uraniumbased fuels.40 Analysis with N, N-dimethyl-N, N-dioctyl-hexylethoxy-malonamide (DMDOHEMA), seen in Figure 1-4, has shown that because of incr eased lipophilicity, it is highly resistant to hydrolysis and radiolysis.41 In another recent study, the efficiency of N, N, N, Ntetraoctyl-3-oxapentane-1,5-diamide (T ODGA) was investigated, and it showed high extractability with trivalent metal ions.42 For the extraction of Eu(III), Am(III), Th(IV), and U(VI), N, N'-dimethyl-N, N'-dihexyl-3-thiop antanediamide (DMDHTPDA) was used as an extractant.43 When used alone, none of the cations were extracted into the organic phase because of very weak complexation due to the presen ce of sulfur atom, a very soft base. Although extraction experiments were performed using syne rgistic thenoyltrifluoroa cetone except with the ion of the Th (IV) system, the separation factor s were smaller for this ligand than those of thenoyltrifluoroacetone and N, N'-dimethyl-N, N'-dihexyl-3-oxapentanediamide (DMDHOPDA)

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30 which is the oxo ethe r analog of DMDHTPDA.43 TODGA and DMDHOPDA are also depicted in Figure 1-4. Earlier, ether type diamides with oxygen or nitrogen introduced into carbon chain between the two amide groups were synthesized and analyzed for their extraction behaviors.37 It was determined that the extractability of diglycolam ide (DGA) for actinides is greater than that of malonamide.44 The ether oxygen in DGA is important fo r chelation to actinides, showing tridentate coordinati on. Another important factor is the lengt h of the alkyl chain attached to the N atom of the amide group, which determines the di stribution ratios and so lubility of the amide in diluent.44 In another study with ether type ligands, extraction experiments were performed with N, N'-dimethyl-N, N'-dihexyl-3-oxapent anediamide, (DMDHOPDA), N, N'-dihexyl-3thiopentanediamide, (DHTPDA), and N,N'-d ihexyl-3-oxapentanediamide, (DHOPDA). Extraction data revealed that no pH de pendence was observed with DMDHOPDA for Eu3+, Am3+, Th4+, NpO2+ and UO2 2+ ions.37 1.4.2.2 SANEX process Nitrogen heterocycles are promising for th e separation of actinides(III) from nuclear waste.45, 46 The ligands 2, 2:6 2-terpyridine and 2, 4, 6-tri(2-pyridyl)-1, 3, 5triazine have been used, and separation factors between Am(III)/Eu(III ) 7 and 12 were obtained, respectively. These ligands required a weak organic acid as synergist.8, 46 The most efficient ligands are the ones bearing e ither 1, 2, 4-triazine or 1, 2, 4-triazole groups incorporated into a tridentate ligand.47 Alkylated 2, 6-di(1, 2, 4triazin-3-yl)pyridines (BTP) have been reported to be very powerful extractants.8, 9, 22, 4550 These ligands are able to attain separation factors for amer icium or curium versus europium of more than 100 in up to 1 M nitric acid solution.8, 45, 47, 49 The structure for BTP is given in Figure 1-5.

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31 The reason for the high selectivity of these lig ands is may be the soft donor nitrogen atoms form stronger bonds with the more covalent actinides.22, 46, 48 The electron density on the nitrogen atoms and the basic character of these ligands are the main fact ors for the coordination of the metal ions with these ligands.47 During extractions, the liga nd coordinates to the metal through the nitrogen of its central pyridine and the nitroge n atoms at the 2-position of the triazinyl rings.22 The ligand forms [ML3]3+ type cations which enab le the phase transfer possible.47 A recent study brings up a different explanation for the selectivity of these ligands. The greater thermodynamic stability of the actin ide complexes in relation to that of the lanthanide complexes may be responsible.45 Also 2, 2:6, 2-terpyridine, 2, 4, 6-tris(4-alkyl-2-pyr idyl)-1, 3, 5-triazine and 4-amino-bis(2, 6-(2-pyridyl))-1, 3, 5-triazine, were tested as extractants, and a variety of separation factors for actinides over lanthanides were achieved.9 The ligand structures are shown in Figure 1-5. Since 2, 6-di(5, 6-dialkyl-1, 2, 4-triazin-3-yl)pyridines are su sceptible to hydrolysis and radiolysis, different ligand systems with 2, 6-dioxadi azolylpyridines, as seen in Figure 1-5, were synthesized as mimics with the hope of overc oming the hydrolysis and radiolysis problems.47 Although varying separation factors were achieved, these extractants were not as efficient as 2, 6-bis(5, 6-dialkyl-1, 2, 4triazin-3-yl)pyridines.47 Also, extractant systems with 2, 6-bis (benzi midazol-2-yl) pyridine were synthesized but the separation factors were not higher than 23.51 1.4.3 Pre-organized Ligand Systems for Nuclear Waste Processing Preorganization of a ligand makes complexation to the target metal ion more facile since it is already placed at a certain position that can collaborately work with the other ligating sites already positioned.52 The system predisposed to the high number of coordination sites required by the metal cation. The preorganized ligand syst ems are better extrac tants due to entropic

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32 factors.2 The limited flexibility of the coordinating sites favors the coordination to the metal compared to the competing solvent molecules or anions.2 1.4.3.1 Calixarenes Calixarene platforms contain various func tional groups positioned in a well defined arrangement.53 The calixarene platform can be functionalized either at the lower rim surrounding a smaller cavity or at the uppe r rim surrounding a larger cavity.2 The size of the platform depends on the number of phenol groups; calix[3]are ne being the smallest with three phenol groups, and calix[8]arene being one of the biggest with eight phenol groups.2 Increasing the size of the platform makes it more flexible a nd be able to have more conformations.2 Several calixarene systems have been studied for extraction with mono54, 55 and bifunctional phosphine oxides2, 21, 56, 57 in addition to CMPO, the most investigat ed moiety with calixarenes, as seen in Figure 1-6. All the systems studied thus far ha ve indicated that with the preorganization introduced by the calixarene systems, better extrac tions and selectivity are attained compared to the same ligand systems w ithout preorganizations. In addition to phosphorus containing ligands, picolinamide systems have been studied. However, due to protonation at high acidities in these systems, they did not prove to be as interesting for industrial applications.2 1.4.3.2 Cavitands Cavitands are structurally similar to calix arenes except that upper rim phenyl-phenyl eythylene glycol bridges prevent phenyl rings rotation making them more rigid.2 Studies with both CMPO and Cyanex 301 based ligands have been performed with cavitands.2, 52, 58 The structure of a CMPO derivative of a cavitand is depicted in Figure 1-7 Although the extraction of Am(III) was enhanced with a cavitand system bearing CMPO, it was not as effective as the calixarene derivative.2 The selectivity of Eu(III) over UO2(II) and Fe(III) was higher with CMPO

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33 cavitand systems than simple CMPO systems.52 Conversely, tetrakis(phosphane sulfide) cavitands are ineffective for the extraction of Am(III).58 1.4.3.3 Tripodands Tripodands are very flexible C3-symmetric platforms with a central carbon atom to which three identical arms are attached with metal binding s ites. An R group is also attached to the central carbon atom to control the solubility.2 In a recent study reasonable extractions were obtained with Eu (III) and Am (III) with CMPO groups in the presence of a synergistic BrCOSAN with tripodand systems.59 The CMPO tripodand is depicted in Figure 1-7. 1.4.3.4 Trityls Trityl platforms are C3-symmetric platforms with three ph enol groups attached to a single carbon atom from their meta positions. In the tr iphenoxymethane platforms, the oxygens of the phenol groups were determined to be pointi ng up, parallel to the central hydrogen atom.60 Ligands based on the triphenoxymethane platform are advantageous because they can be prepared quickly in bulk quanti ties, the solution and solid state structures of the complexes can be fully characterized, and the solubility properti es can be easily changed by making adjustments to the substituents on the base of the platform. Th is platform can be functionalized either at the oxygen atom of the phenol group (upper side func tionalized triphenoxymeth ane platform) or at the paraposition (lower side functio nalized triphenoxymethane platform). A tris CMPO ligand system was developed with the upper side functionalized triphenoxymethane platform.61 The crystal structures of Th(IV) and Nd(III) clearly indicated the coordination of the preorganized CM PO ligands through C=O and P=O groups.61 In simulated waste extractions, the ligand system showed a high affinity for Th(IV) but very low affinity for the lanthanide (III) series.61 The structure of this lig and is shown in Figure 1-8.

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34 Inspired by the upper side functionalized CMPO triphenoxymethane system, Bhmer, et al. introduced a C3-symmetric lower side functionalized CMPO system with triphenoxymethane platform,62 shown in Figure 1-8. This ligand system revealed reasonable selectivity between Am(III) and Eu(III) but it was not as effective as the calixarene systems for extractions from highly acidic media.62 In addition to the CMPO system, another upper side functionalized ligand system was synthesized with DGA as depicted in Figure 1-8.63 In this molecule three diglycolamides are collectively providing nine coor dination sites with their diamide moieties and their etheric oxygen atoms to help to form C3-symmetric metal complexes. This ligand revealed slightly higher selectivity than its simple form between Eu (III) and Am (III). It also had higher affinity for the heavier lanthanide (III) cations th an the lighter ones in dichloromethane.63 When the experiments were repeated with 1-octanol, the ex tractant showed selectivity for the lanthanide ions in the middle of the series. When n-butyl substrates instead of is opropyl substrates were used, the efficiency of the ex traction dropped significantly. The selectivitiy of the ligand was also lost. Extraction experiments with 1-octanol and ndodecane solvents with the n-butyl derivative were unsuccessful due to pha se separation problems. According to the solid state structures obtained with DGA ligand with upperside functionalized triphnoxymethane platform with isopr opyl substrates with Yb, the geometry of the complex is C3 symmetric tricapped trigonal prism with coordination sites of diamide moieties and the oxygen atoms in between. Oxygen atoms are coordinated to the metal and make the tricapped part of the structure. The ligand fully saturated the c oordination sphere of the metal leaving no space for the nitrat e ions to coordinate.

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35 In order to achieve selectivity between the ac tinide and lanthanide ions, the etheric oxygen in the middle was replaced by sulfur to make the thio derivative of the legend. However the extraction experiments revealed th at there were negligibly low distribution coefficients for this ligand. The big sulfur atom was making the geomet ry of the complex to be distorted from the tricapped trigonal prism geometry and resulting with poor metal binding. This also showed the importance of the etheric oxygen in DGA derivative in terms of its binding and its effect for the extraction experiments. The DGA ligand was synthesized with the lo wer side functionalized triphenoxymethane platform but the ligand showed no extraction wi th this type of triphenoxymethane platform. 1.5 The Research Objectives The main goal of this project was to desi gn and synthesize new multidentate ligands by exploiting triphenoxymethane platform, in order to test their extraction be haviors with trivalent lanthanide cations in 1 M nitric acid solutions. The new ligands were to be tested in acid solutions with lanthanide cations to determine the feasibility of their use for actual extraction process of nuclear waste. The research also focu ses on the characterization of the lanthanide (III) complexes both in solution and solid state. Pr eviously in our group, incenerable nonadentate ligand systems bearing DGA groups with triphenoxymethane platform were synthesized and the extraction behaviors of these ligands were studied in detail and it was observ ed that they showed successful extraction performances. Having observe d successful extractio ns with nonadentate DGA ligands with triphenoxymethane platform and the reported success of heterocyclic ligands bearing relatively softer nitrog en atoms led us to design a new incenerable ligand system bearing both pyridine and diamide moieties. To creat e this ligand system three pyridine-2, 6dicarboxamide derivatives were introduced to tr iphenoxymethane platform to form a nonadentate ligand system. Both upper side and lower side functionalized triphenoxy methane ligands were

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36 prepared. Extraction experiments were performed in 1 M nitric acid solution with Ln(III) cations to determine the extractabilities of these metals. Extraction experiments were repeated with chloro-COSAN to enhance the extraction of the la nthanides with the new ligand systems.

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37 Figure 1-1 Schematic representation of a tricapped trigonal prismatic geometry Figure 1-2 Schematic structure of chloro-COSAN ion. Co hexachlorobis(1,2-dicarbollide)cobaltate Cl6COSAN-ion Cl CH BH

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38 P O H3C(H2C)3O O(CH2)3CH3 O(CH2)3CH3 AP O H3C(H2C)7 CH2 O N CH2CH(CH3)2 CH2CH(CH3)2 P O R R R CP O (H3C)2HC(H2C)7O O(CH2)7CH(CH3)2 OH P S R R SH EB D Figure 1-3 Selected phosphorus containing extractants. A) TBP, B) CMPO, C) TRPO, D) DIDPA, E) Cyanex 301.

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39 N O N O ON O N O N O H3C(H2C)5(CH2)7CH3(CH2)7CH3 N C8H17 C8H17 O O O N C8H17 C8H17 O O N O N (CH2)5CH3(CH2)5CH3 E A B C D Figure 1-4 Selected diamide extractants. A) TEMA, B) D2EHIBA, C) DMDOHEMA, D) TODGA, E) DMDHOPDA.

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40 N N N N N N N AN NN NN N NN R N R R NN N NN NH2 N N H N N NH N N O N N O N R R E B C D F Figure 1-5 Selected pyridine bearing he terocyclic extractants. A) BTP, B) 2,4,6-tris(4-alkyl-2pyridyl)-1,3,5-triazine, C) 2,2: 6,2-terpyridine, D) 2,6-bis(be nzimidazol-2-yl)pyridine, E) 4-amino-bis(2,6-(2-pyridyl))-1,3,5-tr iazine, F) 2,6-dioxadiazlylpyridine.

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41 OR OR RO NH HN HN NH OR Ph Ph Ph Ph Ph Ph Ph H2C H2C H2C R R R R H2C HN HNHN HN P O n=1,2,3 O P O P O O O O PO O PO O PO O PO O P O Ph Ph Ph Ph Ph Ph Ph Ph Ph n n n nA B Figure 1-6 Upper and lower rim functionalized calix[4]arenes with CMPO. A) Upper rim functionalized ligand, B) Lower rim functionalized ligand.

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42 O O C5H11 (CH2)nNR O P O Ph Ph n=1,3 R N O P O Ph Ph NR O PO Ph Ph N R O P O Ph Ph O O O R ABFigure 1-7 Cavitand and tripodand systems w ith CMPO. A) cavitand, B) tripodand system O NH O PO Ph Ph 3 O HN 3 O O N O NH O P O Ph Ph O 3 R A B C Figure 1-8 Trityl ligand systems. A) Upper side functionalized triphenoxyme thane platform with CMPO groups, B) Upper side functionaliz ed triphenoxymethane platform with diglycolamide (DGA) groups, C) Lower side functionalized triphenoxymethane platform with CMPO groups.

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43 CHAPTER 2 NEW NONADENTATE LIGANDS AS CAND IDATES FOR ACTINIDE/LANTHANIDE SEPARATION: PYRIDINE-2, 6-DICARBOXAMIDE DERIVATIVES OF THE TRIPHENOXYMETHANE PLATFORM BEARI NG PYRIDINE-DIAMIDE MOEITIES 2.1 Ligand Design In the design of a ligand system for the sepa ration of trivalent actinides from trivalent lanthanides commonly found in nucl ear waste, some important fact ors should be considered. The first is that the ligand must be able to easily bind the metal cation and fulfill the required coordination number of the metal coordination sp here. Since extraction e xperiments are typically performed under highly acidic a nd radioactive conditions, the liga nd should have high radiation and chemical stability.64, 65 Also, the solubility of the ligand should be characterized.64 The main purpose of the project is to design a ligand for in dustrial applications so it is important to consider the ease of its synt hesis and purification and the material cost of the ligand.66 The toxicity of the ligand and its de gradation products are also importa nt factors to be taken into account.66 The main goal of nuclear waste treatment is the selective separation of the relatively more covalent trivalent actinides from trivalent lantha nides. Therefore a ligand system bearing softer donor atoms at its binding site relative to oxygen, su ch as N, or S, will be promising to enhance covalent character at the binding site. Also, in order to not create additional waste, the ligand system should be incinerable. Moreover, a ligand system exploiting preorganization will be more advantageous for the purpose of extractions. Last ly, creating a ligand bear ing a coordination site mimicking that of those ligands previously reported to perform well in terms of extractability and selectivity could be advantageous. Keeping these important requirements in mi nd, we designed a nonade ntate ligand system having three asymmetric N, N-dialkylpyridin e-2, 6-dicarboxamide moieties attached to a

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44 triphenoxymethane platform. The novelty of the li gand stems from the fact that it combines both pyridine and diamide binding sites. As men tioned before for the DIAMEX and SANEX processes, diamides and nitrogen-bearing he terocyclic systems have high extraction and selectivity towards trivalent f-block elements. Our proposed ligand system takes advantage of both pyridine and diamide properties. This incinerabl e ligand system is also preferable due to its preorganization which enables it to provide nine binding sites fo r the metal, with six carbonyl groups (C=O) from diamide moieties and three nitrog en atoms from its pyridine moieties. This is advantageous because trivalent f-block cations prefer high coordination numbers. Another important characteristic of this ligand is that it has soft nitrogen atoms at its binding site to enhance covalent character which confers the se lectivity between the trivalent actinides and lanthanides. The selection of tridentate pyridine-2, 6dicarboxamide (DPA)for extraction purposes stems from the fact that the coordination chemistr y of this ligand with trivalent lanthanides has been extensively studied for its photophysical properties.15, 67-71 Not only does this ligand meet all the requirements for the extractions, it provides an ideal coordination s ite for lanthanide (III) cations. Tridentate ligands of the type N, N, N, N-tetraalkylpyrid ine-2, 6-dicarboxamide bearing both pyridine and diamide groups, pro duce stable lanthanide complexes of the type ML3 3+.67 Solution and solid state struct ural investigations for N, N, N, N-tetraethylpyridine-2, 6-dicarboxamide indicated that in these complexes OC-N (ami de) bonds exhibit considerable double bond character, and that the alkyl residues are situated close to the three fold axis and the metal ion.15 The structure of N, N, N, N-tetraethyl pyridine-2, 6-dicarboxamide is depicted in Figure 2-1.

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45 Tripodal ligands were also synthesized with DPA moieties. Three asymmetric tridentate DPA moieties are connected to th e tris(2-(N-methyl)aminoethyl)amine (TREN) tripod to give a nine-coordinate podand that shows pseudo-tricap ped trigonal prismatic geometry with Ln(III) due to the orientation of the three tridentate ligands.69, 71 A similar type of tripodal ligand was synthesized with tris(3-( N -methylamino)propyl)amine (Me-TRPN).70 In all of th ese studies the stabilities of these complexes in solution were studied in addition to the formation of their protonated adducts in acidic media. The struct ures of TREN and Me-TRPN bearing diethyl derivative of DPA are given in Figure 2-1. 2.1.1 Recently Reported Extraction Studies with Pyridine-2, 6-dicarboxamides Research has been sparingly performed with the pyridine-2, 6-dicarboxamides, DPAs, for nuclear waste separation processes. Therefore limited information is available for these molecules, most of which is qui te recent and can be considered to be preliminary. These studies reveal that DPAs do not extract metals from acidic solutions by themselves. However, in combination with chlorinated de rivative of COSAN, high extrac tions of Cs and actinides are achieved.72 DPAs are weaker donors than malonamides. Th ey also are less basi c in character than picolinamides because the second carboxamide group introduced into the molecule further decreases the basicity of the pyridine nitrogen.73 Smirnov et al. worked on derivatives of DPA including tetraethyl DPA, tetran -butyl DPA, N, N-diphenyl-N, Ndimethyl DPA, N, N-diheptyl DPA and tetrai -butyl DPA.73 The structures of these ligands are depicted in Figure 2-2. All of these extractan ts showed moderate extraction of Am in nitric acid solution w ith metanitrobenzotrifluoride as diluent. However, when chloroCOSAN is used, the distribution ratio (DAm) for Am is quite high (>~10), which is comparable to CMPO extractions. Another importa nt factor is the selectivit y for Am over Eu. Depending on

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46 their results the separation factor is DAm/DEu 2.6 for tetran -butyl DPA which indicates that the system has potential for Am/Eu separation. The pyr idine nitrogen is the li kely reason for this selectivity.73 Based on this data, DPAs have been propos ed as a potential alternative to CMPO for the extraction of actinides.73 In another study, N, N-diethyl-N, N-di (p -tolyl) DPA showed good extraction properties in nitric acid with metanitrobenzotrifluoride as diluent.74 This ligand extracts Am better than Eu. However, separation factors decrease with incr easing solution acidity. Even 0.2 M of N, Ndiethyl-N, N-di (p-tolyl) DPA is sufficient enough to recover Am and is considered to be a promising candidate for the separation process.74 The structure of this ligand is also given in Figure 2-2. In order to probe the effect of acid conditions, extractions wi th DPA were carried out in perchloric acid with fluorinated solvents as the diluents.75 The extraction efficiency is much higher in perchloric acid than in nitric aci d. The extraction ability is dependent up on the substituents on the nitrogen atoms, such that dialkyldiaryldiamides turn ed out to be better extractant than diand tetraalkyldiamides for Am and Eu. In spite of high extraction performances in perchloric ac id, the selectivity is lost.75 2.1.2 Research Objectives In this study, two derivative s of DPA were introduced to derivatives of both upper and lower side functionalized triphenoxymethane pl atforms to form unsymmetrical nonadentate ligands for extraction purposes. These ligands were fully characterized and both their solid state and solution structures were analyzed. Extracti on experiments were performed in three different solvents (1-octanol, 1, 2-dichloro ethane and dichloromethane), with lanthanide (III) cations in 1 M nitric acid solution.

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47 In this chapter the synthesis of these ligands will be described in detail. In the following chapter the extraction experiments will be explained and the results of these experiments will be discussed in detail and compared to re cently reported studies involving DPAs. 2.2 Synthesis of the Nonadentate Ligand Systems The key step of the synthesis of the ligands was the coupling reaction between the amine groups of the triphenoxymethane platform and the carboxylic acid of the 6-(N, N,dialkylcarbamoyl)pyridine-2carboxylic acid. For this purpose upper and lower side functionalized triphenoxymethane platforms with amine groups were synthesized in addition to the 6-(N, N, dialkyl-diarbamoyl)pyr idine-2-carboxylic acid derivatives. 2.2.1 Synthesis of Triphenoxymethane Platforms with Amine Groups The upper side functionalized triphenoxymethane platforms, with three carbon linker groups, ( 2-1) ,76 and two carbon linker groups, ( 2-2) ,77 were synthesized as reported. A synthetic route was developed to make the lower side f unctionalized triphenoxymethane platform with the amine group. First, 2, 2', 2-methanetriyltris(4-nitrophenol) ( 2-3) was prepared according to the literature method.78 In order to synthesize the lower side functionalized triphenoxymethane platform, the phenol group of 2 3 must be protected with an al kyl group. To this end alkylation reactions were performed with a weak base a nd an alkyl iodide, RI, (R= methyl, octyl) The synthetic scheme for these molecules, met hyl protected 2-methoxy-5-nitrophenylmethane ( 2-6) and octyl protected tris(5-nitro-2-(octyloxy)phenylmethane ( 2-7) are depicted in Scheme 2-1. The first method that was used to synthesize 2-6 was to reflux 2-3 with methyl iodide and K2CO3 in acetone for two days fo llowing the literature method.63 However, the yield of this reaction was no more than 30 % which was very low and in convenient for the preparation of a starting material. Another method was tried by stirring 2-3 with methyl iodide and K2CO3 in dry DMF for five days, which yielded 98 % of very clean product. The same method yielded successful

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48 preparation of 2 -7 by using octyl iodide with 65 % yield. For the preparation of 2 -7 another method was also tried by using sodium hydride78 instead of K2CO3 but unfortunately a mixture of unknown products was obtained. The last step of the synthesis of the lower side functionaliz ed triphenoxymethane platform is the reduction of the nitro groups of 2-6 and 2-7 to yield 3,3',3''-methanetriyltris(4methoxyaniline) ( 2-8) and 3,3',3''-methanetriyltr is(4-(octyloxy)aniline ( 2-9) respectively as seen in Scheme 2-1. This was a very challenging task. Va rious aromatic nitro group reduction methods 63, 79-86 were used, and for each method different reaction conditions were applied by changing the amount of the reagents, the temperat ure of the reaction, or the total time of the reaction. However, in terms of the reaction sa fety, obtaining clean compound with high yield, and the cost of the materials used, only one method 85 turned out to be successful in fulfilling all these requirements. According to this method, 2-6 and 2-7 are refluxed with zinc dust and calcium chloride dihydrate in ethanol overnight to obtain 2-8 and 2-9 in 50 % and 62 % yield, respectively. 2.2.2 Synthesis of 6-(N, N-dialkylcar bamoyl)pyridine-2-carboxylic Acid Two derivatives of 6-(N, N-di alkylcarbamoyl)pyridine-2-carb oxylic acid were synthesized, diethyl derivative 6-(N, N-diethylcarbamoyl)pyridine-2-carboxylic acid ( 2-4) and diisopropyl derivative, (N, N-diisopropylcarbam oyl)pyridine-2-carboxylic acid ( 2-5) 2-4 87, 88, 89 was prepared according to the published procedure. Similarly, 2-5 the isopropyl derivative of 2 -4 was successfully synthesized. In Scheme 2-2 the synthetic pathway for 2-5 is given. For the synthesis of 2-5 6-(methoxycarbonyl) picolinic acid is prep ared as described in the literature.87 This molecule is reacted with thionyl chloride to make an acyl chloride, wh ich is reacted with N, N-diisopropyl amine. The final step is sa ponification of the methyl ester using KOH.

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49 2.2.3 Synthesis of the Ligands All the ligands were synthesized by using the coupling reagent; PyBOP.90 This reagent is used for the condensation reacti ons between an amine and a carboxylic acid to form an amide bond. According to the general procedure for the c oupling reactions, the amine derivative of the triphenoxymethane platform was stirred with a 6-(N, N-dialkylcarbamoyl )pyridine-2-carboxylic acid derivative, PyBOP90, and N, N-diisopropyl amine in DMF at room temperature over night. To the reaction mixture, 10 % HCl solution wa s added and stirred for an hour. The resulting precipitate was dissolved in an organic solvent and washed first with 1 M HCl solution, then with 1 M NaOH solution followed by brine soluti on. The organic layer was dried over anhydrous sodium sulfate and filtered. The solvent was removed and the residue was dried. Throughout our studies we worked with tw o different types of triphenoxymethane platforms: upper side functionaliz ed triphenoxymethane platform and lower side functionalized triphenoxymethane platform. The ligands N2, N2', N2 ''-(3, 3', 3''-(6, 6', 6''-methanetriyltris(2, 4di-tert-butylbenzene-6, 1-diyl)tri s(oxy))tris(propane-3, 1-diyl)) tris(N6, N6-diethylpyridine-2, 6dicarboxamide) ( 2-10) N2, N2', N2''-(2, 2', 2''-(6, 6' 6''-methanetriyltris(2,4-di-tertbutylbenzene-6, 1-diyl)tris(oxy) )tris(ethane-2, 1-diyl))tris (N6, N6-diethylpyridine-2, 6dicarboxamide) ( 2-11) and N2, N2', N2''-(2, 2', 2''-(6, 6' 6''-methanetriyltris(2, 4-di-tertbutylbenzene-6, 1-diyl)tris(oxy) )tris(ethane-2, 1-diyl))tris (N6, N6-diisopropylpyridine-2, 6dicarboxamide) (2-12) are the molecules made by us ing upper side functionalized triphenoxymethane platform. The synthetic scheme for 2-10 and 2-11 are depicted in Scheme 23. In Scheme 2-4 the synthetic pathway for 2-12 is shown. The lower side functionalized triphenoxymethane platform was used to prepare N2, N2', N2''-(3, 3', 3''-methanetriyltris(4-methoxybenzen e-3, 1-diyl))tris(N6, N6-diethylpyridine-2, 6-

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50 dicarboxamide) ( 2-13), N2, N2', N2''-(3, 3', 3''-meth anetriyltris(4-methoxybenzene-3, 1diyl))tris(N6, N6-diisopropylpyr idine-2, 6-dicarboxamide) (2-14), and N2, N2', N2''-(3, 3', 3''methanetriyltris(4-(octyloxy)benzene-3, 1-diyl)) tris(N6, N6-diethylpyridine-2, 6-dicarboxamide) ( 2-15) and N2, N2', N2''-(3, 3', 3' '-methanetriyltris(4-(octyloxy) benzene-3,1-diyl))tris(N6, N6diisopropylpyridine-2, 6-dicarboxamide) ( 2-16 ). In Scheme 2-5 the synthetic route for 2-13 and 2-15 and in Scheme 2-6 the synthetic route for 2-14 and 2-16 are depicted. 2.3 Conclusion Nonadentate ligand systems bearing unsymmetr ical pyridine-diamide moieties with both upperand lower-side functionaliz ed triphenoxymethane platform derivatives have been successfully synthesized and characterized. Thei r extraction behaviors with lanthanide (III) cations in 1 M nitric acid solution will be discussed in detail in Chapter 3. 2.4 Experimental Section 2.4.1 General Considerations All solvents and starting materials were purchas ed from Fisher Scient ific and used without purification unless otherwise stat ed. 2, 6-pyridine-dicarboxylic ac id (Aldrich), 1-iodomethane (Fisher), 1-iodooctane (Acros), potassium car bonate (anhydrous) (Fisher), Zn powder (Fisher), CaCl2.2H2O (Acros), Ln(NO3)3.x H2O (Ln= La, Ce, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Er, Tm, Yb) (Aldrich), PyBOP (benzotriazol-1-yl)oxyt ripyrrolidinephosphonium hexafluorophosphate) (Acros), N, N-diethylamine (F isher), N, N-diisopropylamine (F isher), N, N-diisopropylethyl amine (Fisher), were used as obtained. Anhydr ous DMF was used as received for reactions requiring this solvent. 3, 3', 3''-(6, 6', 6''methanetriyltris(2, 4-di-tert-butylbenzene-6, 1diyl)tris(oxy))tripropan-1-amine, 2-176, 2, 2', 2''-(6, 6', 6''-methanetriyltris(2, 4-di-tertbutylbenzene-6, 1-diyl)t ris(oxy))triethanamine, 2-277, and 2, 2', 2''-methanetriyltris(4nitrophenol), 2-363, were synthesized as reported. 6-(N, N-diethylcarbamoyl)pyridine-2-

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51 carboxylic acid, 2-487, 88, 89 was prepared according to the published procedure. Following the same procedure (N, N-diisopropylcarba moyl)pyridine-2-carboxylic acid 2-5 the diisopropyl derivative of 2-4 was successfully synthesized. All 1H NMR spectra were recorded on a Varian VXR-300 or Mercury-300 spectrometer at 299.95 MHz. Elemental analysis was performed at the University of Florida. The mass spectrometry analyses were performed on a Bruker APEX II 4.7 T Fourier Transform Ion Cyclone Resonance ma ss spectrometer (Bruker Daltonics, Billerica, MA). 2.4.2 Synthesis Preparation of 6-(N, N-isopropylcarba moyl)pyridine-2-carboxylic acid, 2-4: 6(methoxycarbonyl)picolinic acid was prepared as reported.87 A solution of 6(methoxycarbonyl)picolinic acid (1.3 g, 7.8 mmol) was prepared with 100 mL dry CH2Cl2, thionyl chloride (34.16 g, 0.287 mmo l) and 0.1 mL of dry DMF and refluxed for 1 h. Volatiles were removed under vacuum. The remaining solid was dissolved in 100 mL dry CH2Cl2 and N, N-diisopropyl amine (7.265 g, 71.8 mmo l) was added dropwise under N2 atmosphere. The solution was refluxed for 90 minutes afte r which N, N-diisopropyl amine and CH2Cl2 were removed under vacuum. The crude produc t was dissolved in 100 mL of CH2Cl2 and washed with half saturated NH4Cl solution. The aqueous phase was back-extracted with CH2Cl2 (3 x 100 mL). The combined organic phases were washed with saturated KHCO3 solution. After drying the organic layer with Na2SO4, the solvent was removed and the residue was dried. The crude oily brown residue was dissolved in 50 mL 1 M KOH solution and stirre d for 10 minutes. The aqueous phase was washed with chloroform (2 x 100 mL) and was then ac idified with 25% HCl solution to pH=2. A white compound precipitated out of the solution at pH=2. The product was collected by filtration and dried. Yield: 1.40 g (78 %). 1H NMR (CDCl3) : (ppm) 1.21 (6H, d, 3J = 6.6 Hz, CHCH3), 1.57 (6H, d, 3J = 6.9 Hz, CHCH3), 3.59 (1H, hept., 3J = 6.63 Hz. CHCH3),

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52 3.73 (1H, hept., 3J = 6.8 CHCH3 ), 7.73 (1H, dd, 3J = 7.8 Hz, 4J = 0.9 Hz, Py-H), 8.05 (1H, t, 3J = 7.8 Hz, Py-H), 8.25 (1H, dd, 3J = 6.9 Hz, 4J = 0.9 Hz, Py-H). Calculated for C13H18N2O3: C 62.38, N 11.19, H 7.25. Found: C 62.13, N 11.06, H 7.35. ESI-FT-ICR-MS m/z 273.1225 for [C13H18N2O3+Na]+. Expected: 273.1210. Preparation of tris(2-methoxy5-nitrophenyl)methane, 2-6: A mixture of 2, 2', 2''methanetriyltris(4-nitrophenol), 2-3 (9.30 g, 21.76 mmol), anhydrous K2CO3 (15.04 g, 108.8 mmol), CH3I (15.45 g, 108.8 mmol) and 125 mL of anhydrous DMF was stirred for five days at room temperature. 200 mL of water was adde d and the mixture was stirred for 1 h. The precipitate was collected by f iltration, washed with water and dried. Yield: 10.05 g, (98 %). 1H NMR (CDCl3): (ppm) 3.84 (9H, s, OCH3), 6.25 (1H, CH), 6.99 (3H, d, 3J = 9.0 Hz, Ar-H), 7.66 (3H, d, 4J = 2.7 Hz, Ar-H), 8.25 (3H, dd, 3J = 9.2 Hz, 4J = 2.85 Hz, Ar-H). Calculated for C22H19N3O9: C 56.29, N 8.95, H 4.08; Found: C 56.69, N 8.57, H 3.91. Preparation of tris(5-nitro-2 -(octyloxy)phenyl)methane, 2-7: Similar synthetic methodology was applied to the synthesis of 2-7 2, 2', 2''-methanetriyltris(4-nitrophenol), 2-3 (5.0 g, 11.7 mmol), anhydrous K2CO3 (8.09 g, 58.5 mmol), 1-i odooctane (14.05 g, 58.5 mmol) and 60 mL of anhydrous DMF were stirred for five days at room temperature. 200 mL of water was added and the mixture was stirred for 1 h. Th e oily product was separated from the aqueous part. After washing the thick o il several times with water (3 x 100 mL), it was dissolved in CH2Cl2. The organic solution was washed with water (3 x 100 mL), dried over Na2SO4, and the solvent was removed under vacuum. The resulting thick oil was stirred in 250 mL of pentane for 3 hours. The pure product was filtered from pent ane solution as solid. Yield: 5.80 g, (65 %). 1H NMR (CDCl3): (ppm) 0.85 (9H, t, 3J = 6.9 Hz, OCH2CH2(CH2)5C H3), 1.22 (30H, br, overlapping signal, OCH2CH2 (C H2)5CH3), 1.55 (6H, p, 3J = 5.5 Hz, OCH2C H2(CH2)5CH3), 3.94

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53 (6H, t, 3J = 6.2 Hz, OC H2CH2(CH2)5CH3), 6.24 (1H, s, CH), 6.91 (3H, d, 3J = 9.0 Hz, Ar-H), 7.69 (3H, d, 4J = 2.7 Hz, Ar-H), 8.19 (3H, dd, 3J = 9.2 Hz, 4J = 2.9 Hz, Ar-H). Calculated for C43H61N3O9: C 67.69, N 5.50, H 8.05. Found C 67.60, N 5.49, H 8.21. Preparation of 3,3',3''-methanet riyltris(4-methoxyaniline), 2-8 This molecule was prepared following a literature pro cedure with a slight modification.85 Tris(2-methoxy-5nitrophenyl)methane, 2-6 (1.0 g, 2.13 mmol), was dissolved in 125 mL of absolute ethanol. Zn dust (14.46 g, 221 mmol) was added to the so lution. While stirring the mixture, CaCl2.2H2O (1.156 g, 7.86 mmol) was dissolved in minimum vol ume of water and added slowly to the mixture. The final mixture was refluxed overnight. The solution was then filtered and the solids were washed with ethanol. Saturated NaHCO3 solution (200 mL) was adde d to the filtrate, which was then stirred for 30 minutes. Th e solution was extracted with CH2Cl2 (2 x 200 mL). The organic layer was washed with water (3 x 200 mL), dried over Na2SO4, and the solvent was removed to give 2-8 as solid. Yield: 0.40 g, (50 %). 1H NMR (CD3CN): (ppm) 3.56 (9H, s, CH3), 3.66 (6H, br, Ar-NH2), 6.12 (3H, d, 4J = 3.0 Hz, Ar-H), 6.13 (1H, s, CH), 6.44 (3H, dd, 3J = 8.3 Hz, 4J = 2.9 Hz, Ar-H), 6.69 (3H, d, 3J = 8.7 Hz, Ar-H). Calculated for C22H25N3O3: C 69.64, N 11.07, H 6.64; Found: C 69.54, N 10.85, H 6.78. Preparation of 3, 3', 3''-methanet riyltris(4-(octyloxy)aniline, 2-9: The synthetic route for 2-9 was very similar to that of 2-8 with the exception that higher mole ratio of Zn dust and CaCl2.2H2O were used. After prepari ng a solution of tris(5-nitro -2-(octyloxy)phenyl)methane, 27 (1.0 g, 1.309 mmol), Zn dust (10.27 g, 157 mmol) in 125 mL of ethanol, CaCl2.2H2O (1.32 g, 8.98 mmol) solution, prepared in minimum amount of water, was added dropwise. The resulting solution was refluxed over night. The solution wa s filtered and washed with ethanol. A 200 ml saturated solution of NaHCO3 was prepared and added to the filtrate. The final solution was

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54 stirred for 30 minutes. The solution was extracted with CH2Cl2 (2 x 200 mL). The organic layer was extracted with water (3 x 200 mL) and dried over Na2SO4. The solvent was removed to dryness to give 2-9 Yield: 0.55 g, (62 %). 1H NMR (CD3CN): (ppm) 0.87 (9H, 3J = 6.8 Hz, OCH2CH2(CH2)5C H3), 1.26 (30H, br, two broad overlapping peaks OCH2CH2 ( CH2)5CH3), 1.54 (6H, br, OCH2C H2(CH2)5CH3), 3.63 (6H, br Ar-NH2), 3.71 (6H, t, 3J = 6.5 Hz, OC H2CH2(CH2)5CH3), 6.10 (3H, d, 4J = 3.0 Hz, Ar-H), 6.28 (1H, s, CH), 6.39 (3H, dd, 3J = 8.4 Hz, 4J = 2.7 Hz, Ar-H), 6.63 (3H, d, 3J = 8.7 Hz, Ar-H). Preparation of N2, N2', N2''-(3, 3', 3''(6, 6', 6''-methanetri yltris(2, 4-di-tertbutylbenzene-6, 1-diyl)tris(oxy))t ris(propane-3, 1-diyl))tris (N6, N6-diethylpyridine-2, 6dicarboxamide), 2-10: A mixture of 6-(N, N-diethylca rbamoyl)pyridine-2-carboxylic acid, 2-8 (0. 93 g, 4.13 mmol), PyBOP90 ( 2.39 g, 5,57 mmol), N, N-diisopr opylethylamine (1.38 mL, 8.33 mmol) and 3, 3', 3''-(6, 6', 6''-methanet riyltris(2, 4-di-ter t-butylbenzene-6, 1diyl)tris(oxy))tripropan-1-amine, 2-1 1.00 g, 1.25 mmol) was stirred in anhydrous DMF (25 mL) at room temperature for 22 hours. 100 mL of 10% HCl solution was added and the mixture was stirred for 1 hour. The resulting precipitate wa s isolated by filtration and then dissolved in ether. The ether solution was wa shed with 1 M HCl solution (3 x 200 mL), 1 M NaOH (3 x 200 mL), and finally once with 200 mL of brine solution. The organic la yer was dried over Na2SO4 and concentrated. The resultant oily residue was treated with a few milliliters of pentane and a few drops of acetone and the product precipita ted as a white solid. Yield: 0.98 g, (56 %). Diffusion of pentane into an ether solution of the ligand gave crystals suit able for X-ray analysis. 1H NMR (CDCl3) : (ppm) 1.12 (9H, t, 3J = 7.2 Hz, CONCH2C H3), 1.18-1.23 (coinciding peaks 9H, t, CONCH2CH3 with 27H, s, Ar-(CCH3)3) ,1.34 (27, s, Ar-C(CH3)3), 2.16 (6H, p, 3J = 6.9 Hz, Ar-O(CH2C H2CH2)NH), 3.25 (6H, q, 3J = 7.2 Hz, CONC H2CH3 ), 3.46 (6H, q, 3J = 7.2

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55 Hz, CONC H2CH3), 3.62 (6H, t, 3J = 6.1 Hz, Ar-O(C H2CH2CH2)NH), 3.73 (6H, q, 3J =7.3 Hz, Ar-O(CH2CH2C H2)NH), 6.44 (1H, s, CH), 7.17 (6H, s, Ar-H), 7.64 (3H, dd, 3J = 7.6 Hz, 4J = 1.2 Hz, Py-H), 7.90 (3H, t, 3J = 7.7 Hz, Py-H), 8.17 (3H, dd, 3J = 7.7 Hz, 4J = 1.0 Hz, Py-H), 8.24 (3H, t, 3J = 5.7 Hz, Ar-O(CH2CH2CH2)N H ). Calculated for C85H121N9O9: C 72.26, N 8.92, H 8.63; Found: C 72.02, N 8.77, H 8.86. ESI-FT-ICR-MS m/z 1412.9371 for [C85H121N9O9+H]+. Expected:1412.9321. Preparation of N2, N2', N2''-(2, 2', 2''(6, 6', 6''-methanetri yltris(2, 4-di-tertbutylbenzene-6, 1-diyl)tris(oxy) )tris(ethane-2, 1-diyl))tris (N6, N6-diethylpyridine-2, 6dicarboxamide), 2-11: A solution of 6-(N, N-diethylca rbamoyl)pyridine-2-carboxylic acid, 2-8 (0.98 g, 4.39 mmol), 2, 2', 2''-(6, 6', 6''-meth anetriyltris(2, 4-di-t ert-butylbenzene-6, 1diyl)tris(oxy))triethanamine, 2-2 (1.00 g, 1.32 mmol), PyBOP90 (2.51 g, 4.83 mmol) and N, Ndiisopropylethylamine (1.45 mL, 8.79 mmol) was prepared in 25 mL anhydrous DMF and was stirred for 22 hours at room temperature. 100 mL of 10% HCl solution was prepared and added to the mixture. The resulting solution was stir red for 1 hour. The precip itate formed after the addition of HCl solution was filtered and then dissolved in ether. The ether solution was extracted with 1 M HCl solution (3 x 200 mL), 1 M NaOH (3 x 200 mL), and with 200 mL of brine solution. The ether layer was dried over Na2SO4 and concentrated. The oily residue was treated with pentane to give pure, white product. Yield: 0.80 g, (44 %). 1H NMR (CDCl3): (ppm) 1.05 (9H, t, 3J = 7.0 Hz, CONCH2C H3), 1.14 (9H, t, 3J = 7.2 Hz CONCH2C H3), 1.22 (27H, s, Ar-(CCH3)3), 1.26 (27H, s, Ar-C(CH3)3), 3.32 (6H, q, 3J = 7.2 Hz, CONC H2CH3 ), 3.45 (6H, q, 3J = 7.1 Hz, CONC H2CH3), 3.69 (6H, v. br. s. OCH2C H2), 4.31 (6H, v. br. s. OC H2CH2), 6.66 (1H, s, CH), 7.17 (3H, d, 4J = 2.3 Hz, Ar-H), 7.33 (3H, d, 4J = 2.6 Hz, Ar-H), 7.66 (3H, dd, 3J = 7.9 Hz, 4J = 1.2 Hz, Py-H), 7.91 (3H, t, 3J = 7.9 Hz, Py-H), 8.27 (3H, dd, 3J = 7.7 Hz, 4J

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56 = 1.0 Hz, Py-H), 8.52 (3H, t, 3J = 6.0, Ar-O(CH2CH2CH2)N H ).Calculated for C82H115N9O9: C 71.84, N 9.20, H 8.46; Found: C 71.37, N 8.93, H 8.71. ESI-FT-ICR-MS m/z 1369.8822 for [C82H115N9O9]+. Expected: 1369.8818. Preparation of N2, N2', N2''-(2, 2', 2''(6, 6', 6''-methanetri yltris(2, 4-di-tertbutylbenzene-6, 1-diyl)tris(oxy))t ris(ethane-2, 1-diyl))tris(N 6, N6-diisopropylpyridine-2, 6dicarboxamide), 2-12: Starting with 6-(N, N-diisopropylcarba moyl)pyridine-2-carboxylic acid, 2-9 (1.10 g, 4.40 mmol), 2, 2', 2''-(6, 6', 6''-meth anetriyltris(2, 4-di-t ert-butylbenzene-6, 1diyl)tris(oxy))triethanamine, 2-2 (1.00 g, 1.32 mmol), PyBOP90 (2.52 g, 4.83 mmol) and N, Ndiisopropylethylamine (1.45 mL, 8.7 9 mmol) a solution was prepar ed in 25 mL anhydrous DMF. After stirring the solution for 22 hours at room temperature, 1 00 mL of 10% HCl solution was added. The final solution was stirred for 1 hour. A precipitate formed after the addition of HCl solution which was then filtered and dissolved in ethyl acetate. The ethyl acetate solution was washed with 1 M HCl solution (3 x 200 mL), 1 M NaOH (3 x 200 mL), and finally with 200 mL of brine solution. After drying the ethyl acetate layer over Na2SO4, the solvent was removed. The oily residue was treated with pentan e to give pure, white solid product, 2-12 Yield: 1.24 g, (65 %). 1H NMR (CDCl3): (ppm) 1.09 (18H, d, 3J = 6.6 Hz, CONCH(CH3)C H3), 1.18 (27H, s, ArC(CH3)3), 1.22 (27H, s, Ar-C(CH3)3), 1.41 ((18H, br, CONCH(C H3)CH3), 3.42 (3H, hept., 3J = 4.4 Hz, CONC H (CH3)CH3), 3.56 (6H, br, Ar-O(CH2C H2)NH), 3.73 (3H, hept., 3J = 5.8 Hz, CONC H (CH3)CH3), 4.39 (6H, br, Ar-O(C H2CH2)NH), 6.62, (1H, s, CH), 7.13 (3H, d, 4J = 2.4 Hz, Ar-H), 7.25 (3H, 4J = 2.4 Hz, Ar-H), 7.21 (3H, dd, 3J = 7.7 Hz, 4J = 1.1 Hz, Py-H), 7.87 (3H, t, 3J = 7.8 Hz, Py-H), 8.23 (3H, dd, 3J = 7.7 Hz, 4J = 1.1 Hz, Py-H), 8.44 (3H, t, 3J = 6.2 Hz, ArO(CH2CH2)N H ). Calculated for C88H127N9O9: C 72.64, N 8.66, H 8.80; Found: C 72.40, N 8.52, H 9.02. ESI-FT-ICR-MS m/z (C88H127N9O9+H)+= 1455.9983. Expected: 1454.9829.

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57 Preparation of N2, N2', N2''-(3, 3', 3 ''-methanetriyltris(4-methoxybenzene-3, 1diyl))tris(N6, N6-diethylpyridi ne-2, 6-dicarboxamide), 2-13: The mixture of 3, 3', 3''methanetriyltris(4-methoxyaniline), 2-6 (1.69 g, 4.45 mmol), 6-(N, Ndiethylcarbamoyl)pyridin e-2-carboxylic acid, 2-8 ( 3.30 g, 14.78 mmol), PyBOP90 ( 8.51 g, 20.17 mmol), N, N-diisopropylethylamine (4.9 mL, 29.57 mmol) was dissolved in 25 mL anhydrous DMF. The solution was stirred at room temperature for 22 hours. To this solution, 100 mL of 10% HCl solution was adde d. After stirring for 1 hour, the precipitate that formed after the addition of HCl solution was removed by filtr ation and dissolved in ethyl acetate. Following the extraction of the ethyl ace tate solution by 1 M HCl solution (3 x 200 mL), 1 M NaOH (3 x 200 mL), and with 200 mL of brine solu tion, the organic laye r was dried over Na2SO4. After removing the solvent, the solid product was washed with methanol then w ith an acetone-pentane mixture, and filtered to give pure solid product, 2-13 Yield: 1.88g, (43 %). 1H NMR (CDCl3): (ppm) 1.04 (9H, t, 3J = 6.9 Hz, NCH2C H3), 1.10 (9H, t, 3J = 7.2 Hz, NCH2C H3), 3.20 (6H, q, 3J = 6.9 Hz, NC H2CH3), 3.39 (6H, q, 3J = 7.1 Hz, NC H2CH3), 3.71 (9H, s, Ar-OCH3), 6.38 (1H, s, CH), 6.61 (3H, d, 3J = 2.4 Hz, Ar-H), 6.91 (3H, d, 3J = 9.0 Hz, Ar-H), 7.71 (3H, dd, 3J = 7.8 Hz, 4J = 1.2 Hz, Py-H), 7.94 (3H, t, 3J = 8.0 Hz, Py-H), 8.13 (3H, dd, 3J = 8.9, 4J = 2.6 Hz, Ar-H), 8.25 (3H, dd, 3J = 7.7 Hz, 4J = 1.1 Hz, Py-H), 9.56 (3H, s, Ar-NH). ESI-FT-ICR-MS m/z (C55H61N9O9 + H)+= 992.4719. Expected: 992.4665. Preparation of N2, N2', N2''-(3, 3', 3 ''-methanetriyltris(4-methoxybenzene-3, 1diyl))tris(N6, N6-diisopropylpyr idine-2, 6-dicarboxamide), 2-14: A mixture of 3, 3', 3''methanetriyltris(4-methoxyaniline), 2-6 (0.59 g, 1.56 mmol), 6-(N, Ndiisopropylcarbamoyl)pyr idine-2-carboxylic acid, 2-9 (1.3 g, 5.19 mmol), PyBOP90 ( 2.92 g, 6.92 mmol), N, N-diisopropylethylamine (1.71 mL, 10.32 mmol) in 25 mL anhydrous DMF was

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58 stirred at room temperature for 22 hours. A 100 mL of 10% HCl solution was prepared and added to the solution. The resulti ng solution was stirred for 1 hour and filtered to separate the precipitate formed after the addition of HCl solution. The pr ecipitate was dissolved in dichloromethane and extracted by 1 M HCl solu tion (3 x 200 mL), 1 M NaOH (3 x 200 mL), and with 200 mL of brine solution. Afte r drying the organic layer over Na2SO4, dichloromethane was removed and the solid residue was washed with methanol to give 2-14 as pure solid. Yield: 0.54 g, (32 %). Diffusion of pentane into a THF solution of the ligand gave crysta ls suitable for X-ray analysis. 1H NMR (CDCl3): (ppm) 1.00 (18H, d, 3J = 6.6 Hz, CONCH(CH3)C H3), 1.34 (18H, d, 3J = 6.6 Hz, CONCH(C H3)CH3), 3.36 (3H, hept., 3J = 6.5 Hz, CONC H (CH3)CH3), 3.71 (9H, s, Ar-OCH3), 3.85 (3H, hept., 3J = 7.2 Hz, CONC H (CH3)CH3), 6.34 (1H, s, CH), 6.50 (3H, d, 3J = 2.7 Hz, Ar-H), 6.90 (3H, d, 3J = 9.0 Hz, Ar-H), 7.65 (3H, dd, 3J = 7.8 Hz, 4J = 1.2 Hz, Py-H), 7.93 (3H, t, 3J = 7.8 Hz, Py-H), 8.18 (3H, dd, 3J = 8.9 Hz, 4J = 2.6. Hz, Ar-H), 8.22, (3H, dd, 3J = 8.1 Hz, 4J = 0.9 Hz, Py-H), 9.61 (3H, s, Ar-NH). ESI-FT-ICR-MS m/z (C61H73N9O9+H)+ = 1076.5643. Expected: 1076.5604. Preparation of N2, N2', N2''-(3, 3', 3''methanetriyltris(4-(octyloxy)benzene-3, 1diyl))tris(N6, N6-diethylpyridi ne-2, 6-dicarboxamide), 2-15: A mixture of 3, 3', 3''methanetriyltris(4-( octyloxy)aniline, 2-7 (0.97 g 1.44 mmol), 6-(N, Ndiethylcarbamoyl)pyridin e-2-carboxylic acid, 2-8 (0.97 g, 4.36 mmol), PyBOP90 (2.50 g, 5.93 mmol), and N, N-diisopropylethylamine (1.44 mL 8.69 mmol) were stirred in 25 mL anhydrous DMF for 22 hours at room temperature. After the addition of 100 mL of 10% HCl solution to the reaction mixture, the resulting mixt ure was stirred for 1 hour. In orde r to separate the precipitate formed after the addition of HCl solution, the solu tion was filtered. The precipitate was dissolved in dichloromethane which was then extracted by 1 M HCl solution (3 x 200 mL), 1 M NaOH (3

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59 x 200 mL), and with 200 mL of brine so lution. The organic layer was dried over Na2SO4 and the solvent was removed. The residue was washed w ith pentane to give brown solid. The brown solid was further purified by column chromatogr aphy by using basic alumina with 4% methanol: ethyl acetate solution. Yield: 0.92 g, (56 %). 1H NMR (CDCl3): (ppm) 0.83 (9H, t, 3J = 6.9 Hz, OCH2CH2(CH2)5C H3), 1.06 (18 H, multiplet coinciding with the broad peak at 1.18, NCH2C H3), 1.18 (30H, br, overlapping with the multiplets at 1.06, OCH2CH2(C H2)5CH3), 1.72 (6H, br, OCH2C H2(CH2)5CH3), 3.21 (6H, q, 3J = 7.2 Hz, NC H2CH3), 3.38 (6H, q, 3J = 7.2 Hz, NC H2CH3), 3.84 (6H, t, 3J = 6.4 Hz, OC H2CH2(CH2)5CH3), 6.49 (1H, s, CH), 6.58 (3H, d, 3J = 3.0 Hz, Ar-H), 6.85 (3H, d, 3J = 8.7 Hz, Ar-H), 7.72 (3H, dd, 3J = 7.8 Hz, 4J = 0.9 Hz, Py-H), 7.94 (3H, t, 3J = 7.8 Hz, Py-H), 8.11 (3H, dd, 3J = 9.0 Hz, 4J = 2.4 Hz, Ar-H), 8.30 (3H, dd, 3J = 8.1 Hz, 4J = 1.0 Hz, Py-H), 9.55 (3H, s, Ar-NH). ESI-FT-ICR-MS m/z (C76H103N9O9+H)+ = 1286.8074. Expected: 1286.7951. Preparation of N2, N2', N2''-(3, 3', 3''methanetriyltris(4-(octyloxy)benzene-3, 1diyl))tris(N6, N6-diisopropylpyr idine-2, 6-dicarboxamide), 2-16: Synthesis of this ligand was also carried out with the common method of the coupling reagent PyBOP.90 A solution with 3, 3', 3''-methanetriyltris(4-(octyloxy)aniline, 2-7 (1.22 g, 1.60 mmol), 6-(N, Ndiisopropylcarbamoyl)pyr idine-2-carboxylic acid, 2-9 (1.37 g, 5.47 mmol), PyBOP90 (3.14 g, 7.45 mmol), and N, N-diisopropylethylamine ( 1.81 mL, 10.92 mmol) was prepared in 25 mL anhydrous DMF and was stirred fo r 22 hours at room temperature. After adding 100 mL of 10 % HCl solution, the final solution was stirred fo r 1 hour. During stirri ng in acid solution, a precipitate formed which was later filtered and dissolved in dichloromethane. The organic layer was washed with 1 M HCl solution (3 x 200 mL), 1 M NaOH (3 x 200 mL), and with 200 mL of brine solution. After the or ganic layer was dried over Na2SO4, the solvent was removed and the

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60 residue was washed with pe ntane and dried to give 2-16 as brown solid. Yield: 1.49 g, (68 %). 1H NMR (CDCl3): (ppm) 0.83 ( 9H, t, 3J = 6.9 Hz, Ar-O(CH2)7C H3), 1.00 (18H, d, 3J = 6.9 Hz, CONCH(CH3)C H3), 1.17 (30H, br, OCH2CH2(C H2)5CH3), 1.33 (18H, d, 3J = 6.3 Hz, CONCH(C H3)CH3), 1.79 (6H, br, OCH2C H2(CH2)5CH3), 3.35 (3H, hept., 3J = 6.4 Hz, CONC H (CH3)CH3), 3.56 (3H, br, hept., CONC H (CH3)CH3), 3.83 (6H, t, 3J = 6.2 Hz, ArOC H2(CH2)6CH3) 6.46 (1H, s, CH), 6.48 (3H, d, 3J = 2.7 Hz, Ar-H), 6.84 (3H, d, 3J = 9.0 Hz, Ar-H), 7.65 (3H, dd, 3J = 7.8 Hz, 4J = 1.0 Hz, Py-H), 7.93 (3H, t, 3J = 7.8 Hz, Py-H), 8.17 (3H, dd, 3J = 8.6 Hz, 4J = 2.6 Hz, Ar-H), 8.22, (3H, dd, 3J = 7.9 Hz, 4J = 1.0 Hz, Py-H), 9.60 (3H, s, Ar-NH). N O O N N N O O N N N 3 N O O N N N 3 ABC Figure 2-1 Structures of A) N, N, N, N-tetraethylpyridine-2, 6-dicarboxamide and its tripodal derivatives with B) TREN and C) Me-TRPN.

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61 N O O N N N O O N N N O O HN NH N O O N N (H2C)6 (CH2)6 N O O N N EA B CD Figure 2-2 Structures of some recently studied DPA ligands.A) tetra-n-butyl DPa, B) N,Ndiheptyl DPA, C) tetra-i-but yl DPA, D) N, N-diethyl-N.N-di(p-tolyl) DPA, E) N,N-diphenyl-N,Ndimethyl DPA.

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62 NO2 OH 3 5RI,5K2CO3DryDMF,stir5days (R=methyl,octyl) NO2 OR 3 2-3 2-6(R=Methyl) 2-7(R=Octyl) NH2 OR 3 2-8(R=Methyl) 2-9(R=Octyl) Zn,CaCl2.2H2O EtOH refluxovernight Scheme 2-1 Reaction scheme for th e synthesis of 2-6, 2-7, 2-8 and 2-9. N O O MeO OH 1.SOCl2,DMF,CH2Cl22.N,N-diisopropylamine CH2Cl23.1MKOH N O O N OH 6-(methoxycarbonyl) picolinicacid 2-5 Scheme 2-2 Synthetic scheme for 2-5.

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63 O NH2 3 2-1(n=2) 2-2(n=1) N O O N HO 2-4 Pybop,N,N-diisopropylethylamine DryDMF stirovernight n=1,2 O NH 3 N O O N 2-10(n=2) 2-11(n=1) n=1,2 n n Scheme 2-3 Synthesis of 2-10 and 2-11. O NH2 3 2-2(n=1) N O O N HO 2-5 Pybop,N,N-diisopropylethylamine DryDMF stirovernight O NH N O O N 2-12 3 Scheme 2-4 Synthetic scheme for 2-12.

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64 OR NH2 3 2-8(R=Methyl) 2-9(R=Octyl) OR NH 3 O N O N N O O HO N 2-4 Pybop,N,N-diisopropylethylamine DryDMF stirovernight 2-13R=methyl 2-15R=octyl Scheme 2-5 Synthesis of 2-13 and 2-15. OR NH2 3 2-8(R=Methyl) 2-9(R=Octyl) OR NH 3 O N O N N O O HO N 2-5 Pybop,N,N-diisopropylethylamine DryDMF stirovernight 2-14(R=Methyl) 2-16(R=Octyl) Scheme 2-6 Synthesis of 2-14 and 2-16.

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65 CHAPTER 3 EXTRACTION EFFICIENCIES OF C3-SYMMETRIC NONADENTATE LIGAND SYSTEMS WITH LANTHANIDE (III) CATIONS IN ACIDIC MEDIUM 3.1 Introduction Treatment of highly radioactive nuclear wast e is a challenging scientific problem. The reason that makes it so challenging is that high ly acidic waste contains chemically similar trivalent lanthanide and actinide cations as a mixture which makes the transmutation of the actinides impossible. Scientific research studies have been focused on developing new methods for the separation of these metal ions. Although numer ous extractants have been developed for the selective separation of ac tinides from lanthanides in highly ac idic media, none of the extractants has been suitable for industrial processing. In or der to be applicable for industrial processing a ligand must be incinerable, stable both to acidi c and highly radioactive co nditions, and be able to extract actinides selectively and quantitatively fr om nuclear waste. The extractants that have been studied so far lack one or two of these requirements for the nuclear waste treatment. Since water and/or acid coordi nation and the solubility of the metal complex in the organic phase are also important factors in extractions, it is not possibl e to predict how efficient the target ligand will be without doing the extraction experiments. As a result, the research towards a proper ligand is a trial and error process invo lving extraction experime nts with each ligand prepared. Extraction experiments are perf ormed in acidic solutions containing actinides and/or lanthanides that mimic nuclear waste solutions. The extractant is dissolved in an immiscible organic solvent and is expected to react with th e metal ions when in contact with the aqueous phase and in this way pull the me tals into the organic layer.

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66 In the previous chapter, C3-symmetric nonadentate ligand sy stems with asymmetric DPA groups bearing both pyridine and diamide groups we re introduced. The goal of this ligand design was to take advantage of both the pyrid ine and diamide groups for their individual extraction properties reported in the literature in addition to the advant age of preorganization imported by introducing them to the triphenoxymethane platform. In this chapter the results of the extraction experiments with all the prepared ligands are discussed. The effect of different types of triphenoxymethane platforms were also analyzed for the extraction experiments. NMR scale extraction experiment s were performed with 2-13 and the results will be presented for this experiment. Two metal complexes of 2-10 were prepared and the cr ystal structures of these complexes will be depicted as well as solid state structures of 2-10, 2-13 and 2-14 Extraction experiments were performed in three different solv ents for each ligand. In order to see the effect of a synergist, extraction experiments were al so performed with COSAN solutions. The results with and without COSAN will also be discussed in this chapter. 3.2 Results and Discussion 3.2.1 Extraction Experiments Extraction experiments were performed according to the given procedure.77 For the extraction experiments st andard solutions of 1x10-4 M lanthanide (III) we re prepared in 1 M nitric acid solution. A total of eleven cations from the lanthani de series were used for the extractions which are La, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Er, Tm, and Yb. Their concentrations were determined by UV-Vis spectroscopy at 655 nm with Arsenazo (III) salt. Arse nazo (III) salt is a dye with which lanthanide (III) ions form co mplexes at 2.8 pH. These complexes have an absorbance at 655 nm enabling determination of the concentrations of the complexes. For the extraction experiments not involving COSAN, 1x10-3 M ligand solutions were prepared in either CH2Cl2 or 1-octanol. Extraction experiments in volving COSAN required 1, 2-dichloroethane

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67 because COSAN is obtained as cesium salt (Cs(COSAN), hexachlorobis (1, 2dicarbollide) cobaltate cesium salt) which is soluble in this so lvent. To increase the solubility of COSAN for the extraction experiments, the cesium COSAN sa lt must be converted in HCOSAN. For this purpose, the required amount of Cs (COSAN) was dissolved in 1, 2-dichloroethane, and this solution was extracted repeatedly with 3 M H2SO4 solution to produce HCOSAN. Once HCOSAN solution was prepared, the required amount of ligand was dissolved in this solution to prepare the HCOSAN-ligand mixture. Equal volumes of the organic phase and the aqueous phase were shaken together for 16 hours. After phase separation, Arse nazo (III) solutions of the aque ous layer were prepared and the concentrations of the remaining lanthanide s in the aqueous layer were determined. The extraction percentages were calcula ted with the formula: %E = [(A1 A)/ (A1A0)] x 100. In this equation A0 is the absorbance of 1 M nitric acid solution without any metal, A1 is the absorbance of the solution before extraction and A is the absorption after the extraction. The distribution ratios of the metals were calculated as well with the following formula: D= Morg/Maq. The extraction experiments were repeated three times to test their reproducib ility. All the extraction data for each of the ligands is included in Appendix A. 3.2.2.1 Extraction properties of the ligands with the upper side functionalized triphenoxymethane platform Two different derivatives of the upper side functionalized triphenoxymethane platform were used for the synthesis of the ligands. The first derivative, 2-1, is more flexible with three carbon linkers between the platform and the co ordination site and the second derivative, 2-2, is more rigid having two carbon linkers between the platform and the binding site. By using these platforms, ligands 2-10 2-11 and 2-12 were synthesized. Both 2-10 and 2-11 have ethyl substituents. On the other hand 2-12 synthesized with the two car bon linker triphenoxymethane

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68 derivative, has isopropyl substituents. The isoprop yl derivative was prepared to increase the lipophilicity of the lig and. In this way the solubilities of the complexes formed during the extractions were expected to increase in the organic phase. All these ligands showed similar extraction behaviors. They moderately extracted the lanthanides in CH2Cl2 solution. Experiments were performed with 1x10-3 M ligand and 1x10-4 M Ln concentration. Performing an experiment with 100:1 ratio of 2-10 to Ln (III) did not make any change and the extraction was still poor. To observe the solven t effect, the same extractions with 10: 1 ligand to metal ratio we re repeated in 1-octanol with 2-10 However, the extraction percent was approximately zero in this solvent. These expe riments confirmed that these molecules did not extract metals from aci dic solution efficiently when used alone. To investigate the effect of a synergist, an extraction experiment was performed with ligand 2-10 using COSAN in 1, 2-dichlo roethane solution. In this experiment metal to COSAN to ligand ratios were 1: 10: 100. Unfortunately, there wa s not any extraction with this ligand even in the presence of COSAN. 3.2.2.2 Extraction properties of the ligands with the lower side functionalized triphenoxymethane platform In the literature it is reported that extraction properties of th e calixarenes change depending on the functionalization of the upper (wide) or lower (narrow) rim.2 The extraction performances of wide rim functionalized cal ixarenes with CMPO groups we re better than narrow rim functionalized calixarenes. The reason for this difference was believed to be the greater flexibility of the CMPO moieties provided by the wide rim when compared to the narrow rim.2 Similarly, for the triphenoxymethane platform with CMPO ligand, extrac tion studies with both upper side functionalized77 and lower side functionalized 63 platforms were performed. To see the effect of using different type of platform two different derivati ves of the lower side

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69 functionalized triphenoxymethane platforms were prepared. One of them has methyl protecting group and the other one has the octyl protecting group. The second one is more liphophilic than the first. For each of these platforms, both ethy l and isopropyl derivatives of the ligands were synthesized. Ligands 2-13 and 2-15 are the ethyl deriva tives of the methyl protected and octyl protected platforms, respectively. Ligands 2-14 and 2-16 are the isopropyl derivatives of methyl and octyl protected platforms. The liphopilic ity of the ligands in creases in the order 2-13 < 2-14 < 2-15 < 2-16 The extraction experiments revealed that none of these ligands shows any extractability towards lanthanide (III) ions when used al one with 10: 1 ligand to metal ratio in CH2Cl2. They showed very similar behaviors to the upper side functionalized ligands. However, as indicated previously, Smirnov et al also observed the same behavior with Daps. Ligands 2-15 and 2-16 are the bulkiest ligands which makes them the most liphophilic ligands in the series. Extraction experiments with thes e two ligands were pe rformed in 1-octanol solution, in hopes of making the extracted metal complexes sol uble in the organic phase to achieve better results. However, none of the ligands showed any extraction in 1-octanol. As none of the ligands extracted lanthanide (III) ions from acidic solutions when used alone, extraction experiments with the syne rgist COSAN were performed. According the experiments performed with COSAN in 1, 2-dichloroethane, except for 2-16 all the lower side functionalized ligands showed extractability. Th e efficiency of the extractions depends on the ratios of the COSAN: ligand: metal. 2-13 and 2-15 extract lanthanides 100 % without selectivity with 30: 10: 1 ratio of COSAN: ligand: metal. Ho wever, when the ratio is 10: 1: 1, the extraction efficiencies of the ligands tend to drop. In the extraction data that are given for 2-13 2-14 and 215 for 1x10-3 M COSAN, 1x10-4 M ligand and 1x10-4 M Ln the distribution ratios for 2-13 show

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70 slight selectivity between the li ghter and the heavier lanthanide s. The distribution ratios of 2-14 are similar to that of 2-13, but the selectivity is appare ntly better. In the case of 2-15 there is moderate extraction even in th e presence of COSAN with the same concentration. Extraction experiments with the same conditions were performed for 2-16 as well, but this ligand did not show any extraction efficiency. These results indicate that the extraction pe rformances of the liga nds strongly depend on the amount of the synergist used and the type of the lower side functiona lized triphenoxymethane platform. The platform with the methyl protect ing group works efficiently both with the ethyl derivative, 2-13 and the isopropyl derivative, 2-14 However, with the octyl group protected platform, the efficiency drops significantly with 2-15 and the extraction ability becomes almost zero with 2-16 under the same conditions. Insolubility of the metal complex being formed during extraction is the most likel y reason for the problems related to the extractions with these ligands. In case of 2-15 although it shows moderate extrac tion with low concentration of COSAN and ligand concentration, when COSAN a nd ligand amounts are increased, it extracts metals 100 %. In order to determine the extraction abilities of 2-15 and 2-16 in different solvents extractions were performed in 1-octanol solutio n with COSAN. Neither of the ligands showed any extraction under these conditions. These results clearly show that extraction effi ciencies of the ligands are strongly dependent on the type of the triphenoxymethane platform, the concentration of the s ynergist and the solvent used during the extractions. Due to the high extracti on abilities of 2-13 2-14 and 2-15 under specific conditions mentioned for this particular ligand, these ligands are li kely to be successful

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71 candidates for the nuclear waste treatment. Theref ore extraction experiments with the actinides must be performed to see their extracti on capabilities with these metal cations. According to the results of Smirnov and hi s coworkers, DPA ligands show successful separations between the actinide (I II) and lanthanide (III) cations. It is probable that our ligand systems, taking advantage of preorganization with the same moieties, may be even more successful for selectivity and distribution ratios. 3.2.2.3 Following the extraction efficiency of 2-13 by NMR spectroscopy After having seen the high extraction efficiency of 2-13 with high distribution ratios for the lanthanides, NMR scale extractions were performed with this liga nd with various concentrations of COSAN and the ligand in CD2Cl2. Lutetium was used as the metal because it is diamagnetic and therefore enables monitoring of extractio ns by NMR spectroscopy. First, an NMR spectrum of 1x10-2 M 2-13 solution in CD2Cl2 was taken. The ligand solution was then stirred with 1 M nitric acid solution for two hours. Since extracti ons are performed in strongly acidic solutions, it is possible that protonation or deformation of the ligand may occur. In this case, on the NMR timescale, protonation of the ligand is not observe d. Overlaid spectra for these two particular cases are depicted in Figure 32. Having tested the stability of the ligand in the acid solution, a COSAN-ligand solution was stirred with the metal-containing nitr ic acid solution. To determine the efficiency of the extraction, different concentration ratios were used. When equal concentrations of COSAN, liga nd and metal were used, the extr action did not go to completion according to the NMR spectrum. In addition to the peaks of C3-symmetric species formed, free ligand peaks were also observed. With concentra tions of the ligand and of COSAN at one and a half times that of the metal, the same result with mixture of free ligand and the product was observed. Another trial was performed with the concentrations of both ligand and COSAN being three times that of the metal i on. In addition to the product, th e excess ligand peaks were also

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72 observed. The final trial was using equal concentrat ions of ligand and metal and three fold excess of COSAN. The NMR spectrum is given in Figure 3-1. It can be clearly seen that metal was extracted 100 %. Moreover, the new species formed is a C3-symmetric species. The very top spectrum, a shows the aromatic region of the liga nd before processing with acid. The middle spectrum, b, shows the aromatic region of the ligand af ter stirring in 1 M nitric acid. The last spectrum, c shows the aromatic region of NMR spectru m of the species formed after stirring the 1x 10-3 M metal solution with 3x10-3 M COSAN and 1x10-3 M ligand solution in CD2Cl2. When these spectra are compared, it is seen that the singlet peak for the central carbon hydrogen is shifted from a[[roximately 6.40 ppm to 6.70 ppm after the extraction. The doublet peak originating from the triphenoxymethane platfo rm around 6.80 ppm is shifted to 7.30 ppm. The second doublet seen around 6.95 ppm remains at the same location. The third aromatic peak for the triphenoxymethane platform is shifted fr om 8.02 ppm to 7.20 ppm. Aromatic peaks of the triphenoxymethane platform are not the only peak s shifted after the extraction; the pyridine peaks coming from the DPA groups are also shifted. The doublet of doublets around 7.70 ppm shifted to 8.10 ppm, the triple t peak at 8.00 ppm shifted to 8. 55 ppm and the second doublet of doublet peak shifted from 8.25 to 8.40 ppm for the peaks coming from the of the ligand. The last singlet on the spectra corresponds to the aromatic NH peak. This peak is originally at 9.60 ppm and is slightly shifted to approximately 9.70 ppm after the extraction experiment. The NMR scale extraction experiments clearly s howed the extraction of the metal (III) ions by the formation of the expected C3-symmetric complex. 3.2.3 Solid State Structures of 2-10, 2-13, and [2-10 M]3+, (M=Tm, Yb) The crystal structures of 2-10 and its metal complexes with Tm and Yb are given in Figure 3-2 and Figure 3-3, respectively. Structural and preliminary refi nement data are presented in Table 3-1 and selected bond lengths for the comp ounds are given in Table 3-2. The metals nicely

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73 fit in the nonadentate coordina tion site of the ligand with two carbonyl oxygens and one nitrogen atom on each arm of the tripodal ligand coordinating to the metal. The geometry around the metal for both of the metal complexes is tricappe d trigonal prismatic (TTP). The oxygens of the carbonyl groups at the coordinati on site are located in the tria ngular planes and the pyridine nitrogens that form bonds with the metal cap th e faces of the triangular prism. Both complexes are C3-symmetric. In each of the structures one M (NO3)5 2(M=Tm, Yb) and one NO3 are present as counter ions to neutralize the [ML] 3+ moiety. Binding to the metal has little influence on th e CO bond distance. The bond lengths of LnO (amide) and Ln-N (pyridine) for different complexes of DPA are reported, and these bond lengths are standard with certain values.15 According to the literature the bond lengths for Tb-O with the carbonyl groups is between 2.3562.415 and for the pyridine nitrogen and the metal bond, Tb-N, the given bond lengths are between 2.492.54 When the bond lengths of Tm and Yb with amide oxygen and pyridin e nitrogen are compared with those of N, N, N, Ntetraalkylpyridine-2, 6-dicarboxamide (ONO)-Ln type complexes reported in the literature, there is a close match. Some of the bond lengths are sligh tly shorter than the lite rature data within thud limits of acceptable error. When metal-oxygen (M-O) bond lengths of the [ 2-10 Tm]3+ complex are compared with those of the [ 2-10 Yb]3+ complex, a slight decrease is observed due to the smaller size of Yb relative to Tm. A similar tr end is observed with the metal-nitrogen (M-N) bond lengths of the two complexes. When the metal-oxygen bond lengths at the prism oxygens of the Yb complex are compared with the reported76 metal-oxygen bond lengths of [Yb(H2O)9]3+, it is observed that the metal-oxygen bond lengths are slightly longer in Yb complex than those of the nonaaqua complex. The reported value for the oxygen distances of the [Yb(H2O)9]3+ is 2.302(2)

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74 Table 3-1. X-ray data for the crystal structures 2-10, 2-13, and the metal complexes of 2-10 with Tm and Yb. 2-10 [2-10Tm]3+ [2-10Yb]3+ 2-13 crystal system triclinic triclinic triclinic triclinic space group P-1 P-1 P-1 P1 a () 13.2708 12.3444 12.3925 11.8611 b () 20.2314 20.6250 20.7800 13.7400 c () 34.4564 23.7115 23.7387 18.8106 (deg) 102.395 65.668 65.697 96.6469 (deg) 95.514 76.628 76.299 90.1072 (deg) 98.011 81.309 81.289 97.8883 V c (3) 8871.02 5441.03 5402.77 3015.690 (Mo K ) (mm-1) 0.07 1.84 0.98 0.06 The average distance of the oxygens in the Yb complex is 2.34. Therefore there is only 0.038 difference between the bond lengths of the oxygens. In the case of a previously studied C3-symmetric diglycolamide (DGA) complex this difference is 0.011 .76 In comparing the metal-nitrogen bond distances w ith the equatorial oxygens of the nonaaqua complex, the metalnitrogen bond distance is 0.068 s horter than that of the nonaaqua complex, which is reported to be 2.532(3) The DGA complex however, is reported to have metal-oxygen bond distances 0.103 shorter than the nonaaqua complex. The twist angles between the two triangular pl anes were also determined for both of the complexes. For the Yb complex it is 11.4 and fo r the Tm complex it is 9.6. The trigonal prism is twisted by 15.2 in the Yb3+ DGA and this distortion away from the idealized TTP geometry increases with the size of the metal ion.76 Unfortunately, with 2-13 it was not possible to obtain single crystals with any Ln(III) due to solubility problems. When the two C3 symmetric complexes are compared although DGA ligand is more tightly bonded to the metal cation, the twis t angle, which are the main cr iteria for the deviation from ideal trigonal prismatic geometry, for the DPA complex is lower. Therefore, nonadentate DPA provides a coordination site that is closer to the ideal for (TTP).

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75 The extraction behavior of the nonadentate DGA ligand appears to be related to the distortion angle in such a way th at extraction efficiency dropped with the increase of the twist angle.76 Unfortunately, nonadentate DPA ligand does not show that behavior. When extraction results are considered, 2-10 showed moderate extraction to wards lanthanides even in the presence of the synergistic COSAN. In the DGA system, although the solid state structure showed higher distortion relative to DPA sy stem, the DGA ligand showed high extraction efficiency. To predict of extraction behavior of the ligands another factor can be considered regarding the solid state structures of the ligands. It can be argued that tighter bonding of DGA system to the metal cation relative to DPA system makes th e extraction efficiency higher for DGA system when compared to 2-10. However th is discussion would not be rele vant either because with the DGA system, it was determined in solid structur e that Ce(III) complex has shorter metal-oxygen bond length than Yb (III) complex. The problem is that the extraction efficiency for Ce(III) is less relative to Yb(III) complex which has longe r metal oxygen bond length s and smaller twist angle.76 It is difficult to correlate the extraction behavior of DPA directly to its solid state structure. Lack of crystal structure of th e complexes with other derivatives of the ligand makes it even harder to make a conclusion. The extraction beha vior of the ligand might be more related to solubility issues which will be discussed in the next section. A solid state structure of the lower side f unctionalized triphenoxyme thane platform with the methyl protected derivativ e, with ethyl substituents, 2-13, was obtained.(Figure 3-4). The structure of this ligand is given in Figure 3-4. The X-ray data and the bond lengths of the carbonyl groups are depicted in Table 3-1 and Ta ble 3-2, respectively. In X-ray data, three arms

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76 with the pyridine-diamide moieties attached from the para positions of the phenyl groups of the triphenoxymethane platform are clearly observed. The DPA moieties are attached through their carbonyl groups to the NH groups of the triphe noxymethane platform. In the structure, the methyl groups of the methoxy groups are pointing towa rd the outer part of the platform. In this way they are as far away from each other as possible. Unfortunately, in spite of efforts to crystalliz e metal complexes of this ligand and the other derivatives of the lower side f unctionalized ligands, crys tals suitable for X-ray analysis were not obtained. 3.3 The Factors Affecting the Extraction Pe rformance of Nonadentate Pyridine-2, 6dicarboxamide System Prediction of the extraction behavior of any ligand system is not easy because there are several factors at play. The structure of the ex tracted complex is not actually known. Moreover, the extractions are performed in organic diluentaqueous acidic systems, which increase the factors contributing to the extr action process. There is compet ition between the organic solvent and the water in terms of solvation. There is also competition between the acid proton and the tripositively charged metal cation in terms of acting as a Lewis acid particularly for systems bearing basic groups such as amine or pyridines. All these factors affect the ex traction efficiency of a liga nd. Moreover, since the f-block elements can form complexes with a wide range of coordination numbers, the probability of determining the nature of the extr acted species is low. Above all, the solubility of the ligand in the organic phase and of the re sultant complex in both the aque ous and the organic phase are important to consider.

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77 Table 3-2. Selected bond lengths () for the 210, 2-13, and metal complexes of 2-10 with Tm and Yb. 2-10 [20-10Tm]3+ [2-10Yb]3+ [2-13] C(1) O(1) 1.241 1.246 1.247 1.225 C(2) O(2) 1.244 1.247 1.267 1.235 C(3) O(3) 1.213 1.254 1.256 1.226 C(4) O(4) 1.245 1.234 1.243 1.235 C(5) O(5) 1.264 1.224 1.218 1.228 C(6) O(6) 1.241 1.258 1.222 1.238 M O(1) 2.355 2.324 M O(2) 2.350 2.318 M N(1) 2.490 2.475 M O(3) 2.328 2.326 M O(4) 2.324 2.350 M N(2) 2.471 2.468 M O(5) 2.349 2.358 M O(6) 2.366 2.364 M N(3) 2.464 2.458 The extraction efficiencies of the ligands are strongly dependent on the solvent, the type of triphenoxymethane platform, the liphophilic character of the ligand system and the concentration of the synergist used. Among these, the effect of COSAN is the most important one because none of the ligands show any extraction towards la nthanide ions without COSAN in any solvent. COSAN is acting as a large liphophilic counter ion which renders the resultant complexes soluble in the organic phase such that transfer of the complex to the organic phase is facile. The type of triphenoxymethane platform used is also important. The lip hophilicities of the ligands are closely related to th e type of the tripohenoxymethane platform, which also greatly affects the solubility. All these considerations make the solubility a major factor in the determination of the extraction behaviors of the ligand systems. Starting with the triphenoxymethne platforms used in this study, the mo st polar is the methyl protected lower side functionalized triphenoxymethane platform. Th e second most polar is the octyl protected triphenoxymethane platform, and the least polar is the upper side functionalized

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78 triphenoxymethane platform. The main objective of the extraction experiments in terms of solubility is to provide the right solubility environment for the complex formed. The most efficient ligand system of those studied is th e methyl protected lower side functionalized triphenoxymethane platform with methyl protecti on. The ligands with this platform, both with ethyl and isopropyl derivatives show high extraction performance with almost the same efficiency, the ethyl derivative being slightly mo re efficient than the isopropyl derivative. The extraction efficiency of the octyl derivative drops when compared to methyl protected derivatives under the same extrac tion conditions. The efficiency of the octyl protected ligand with the ethyl substituent is approximately 20%, while the methyl derivative extracts 100 %. The extraction efficiency of the octy l protected triphenoxymethane plat form with isopropyl groups is almost zero. When the concentration of COSAN is tripled, the ethyl derivative of the octyl protected ligand works as efficien tly as the methyl protected liga nds. From this observation it is obvious that the problem is not the matter of having bulkier li gand that prevents the metal coordination, but rather the so lubility. The isopropyl deriva tive of the octyl protected triphenoxymethane platform forms a complex which is too no polar in 1, 2dichloroethane or in CH2Cl2. The same problem occurs with the uppe r side functionalized triphenoxymethane derivatives. Even in the presence of COSAN none of these ligands show any extraction towards lanthanides. Again, complex formed is too nonpolar to be extracted into the organic phase. Another problem of solubility related extraction inefficiencies is due to the solvent itself. In the extractions with 1-octanol none of the ligands showed any extraction for the lanthanides, even in the presence of COSAN. The solvent is very nonpolar, a nd none of the ligands are able to provide the right solubility conditions to work efficiently.

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79 Considering all the factors discussed above, so lubility is most lik ely the reason for the different extraction behaviors of the ligand systems with nonadentate DPA ligand system. Although there are other factors, including different species bei ng formed during the extraction process, and all the important points mentioned in th e beginning of this sec tion, solubility is most likely the one, depending on the experimental data and on the solid state structures of the two complexes discussed earlier. There is one important thing that needs to be pointed out. The DGA system studied previously shows the opposite tr end in terms of extractions depending on the type of the triphenoxymethane platform when compared to DPA system. While the pyridine-2, 6dicarboxamide system shows good extractabili ty with the lower side functionalized tiphenoxymethane system and shows poor extr action with upper si de functionalized triphenoxymethane platform, the DGA system shows no extraction with the lower side functionalized triphenoxymethane platform a nd shows high extraction performance with upper side functionalized triphenoxymethane platform. Th is situation cannot be explained in terms of difficulties with the coordination site binding to the metal cation. Both ligands are capable of coordinating to the metal. The main difference between the two ligands is that DGA is more polar than DPA. Since the extracted comple xes are soluble under only certain conditions depending on the counterions, the triphenoxymethane platform used and the solvent used during extractions, the differences of the polarities of these ligands may be playing an important role in terms of extraction behaviors. As discussed previously, the ideal li gand for high extraction efficiency with the DPA moiety is the methyl protected lower side functionalized triphenoxymethane platform. The other two plat forms make the ligand too non-polar, and they tend to lose their extraction efficiencies. However, when more polar digylcolamide is attached to

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80 the relatively less-polar upper side functiona lized triphenoxymethane platform, the ideal condition is achieved in terms of solubility. However, with the more polar lower side triphenoxymethane platform the ligand is too pola r and looses its extrac tion ability because the metal complex is no longer soluble. Regarding th e DPA system, introducing this relatively more less-polar moiety with respect to DGA to the le ast polar triphenoxymethane platform, the ligand becomes too non-polar to extract the species fo rming during extraction. This discussion stems from the fact that lower side functionalized DP A ligands are soluble in solvents with a narrow range of polarity. As an example, metha nol is too polar to be soluble in for 2-13 and diethyl ether is too nonpolar to be soluble in for the same ligand. If the ligand is behaving this way, the complex formed will act parallel to it, and w ill have narrow range of solubility within the common solvents. 3.3 Conclusion The ligand systems designed, bearing both pyrid ine and diamide moieties providing nine coordination sites with two different types of triphenoxymethane platforms were synthesized. The extraction properties of these ligands indicated that without a synergist they are not efficient. The upper side functionalized tri phenoxymethane platform derivatives of the ligands were not efficient, even in the presence of the synergis t COSAN. However, when the synergist COSAN is used with the lower side functionalized triphenox ymethane platform, the lanthanide cations are extracted up to 100 %. Due to solubility diffe rences, octyl group prot ected triphenoxymethane derivatives are less efficient than the methyl protected triphenoxymethan e platform derivatives. The extraction experiment for 2-13 was repeated on NMR scale and 100 % extraction can be clearly seen from the data when using a ra tio of 3: 1: 1 of COSAN: ligand: Ln. To elucidate the efficiencies of these ligands with actinide (III) cations, experiments should be performed with these cations.

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81 Crystal structures of 2-10 and its metal complexes with Tm and Yb were analyzed. The coordination site has tricapped trigonal pr ismatic geometry. The metal-oxygen and metalnitrogen bond lengths are in ag reement with the literature data. The twist angles of the complexes are approximately 9 and 11 whic h is a negligible deviation from ideal TTP geometry. 3.4 General Procedure for the Pr eparation of [2-10Ln] [Ln(NO3)5] [NO3] (Ln=Tm, Yb) A solution of 0.8 equiv. of Ln(NO3).xH2O in CH3CN was added to a solution of 1.0 equiv. of 2-10 in CH2Cl2 and the mixture was stirred overnigh t. The solvent was removed under vacuum and the solid residue was washed with ethe r and filtered. Slow diffusion of pentane into a CH2Cl2/CH3OH solution of the complexes afforded crystals suitable for X-Ray analysis. [ 2-10 Ln] [Yb(NO3)5] [NO3]: Calculated for C85H121N15O27Yb2: C 48.95, N 9.48, H, 5.89; Found C 49.34, N 9.19, H 6.09. 3.5 X-ray Crystallography The crystal structure analyses of all molecu les were performed by Dr. Michael J. Scott. Unit cell dimensions and intensity data were collected on a Siemens CCD SMART diffractometer at 173 K. The data collections were nominal over a hemisphere of reciprocal space, having a combination of three sets of exposures. Each set with a different angle covered 0.3 in The distance of the crystal to the detector was 5.0 cm. The correction of the data sets for absorption was achieved by SADABS by meas urement of crystal faces. Bruker SHELXTL software package for the PC was used for solv ing the structures by a pplying either direct methods or Patterson functions in SHELXS. Th e space group determinations of the compounds were done from an examination of the systematic absences in the data.

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82 Figure 3-1 NMR scale extracti on data with 2-13. A) 1x10-2 M ligand in CD2Cl2, B) 1x10-2 M ligand after being stirre d in 1 M nitric acid C) C3-symmetric extracted complex formed after the extraction with 1x10-3 M Lu, 3x10-3 M COSAN and 1x10-3 M of 213. a b c

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83 Figure 3-2 Crystal structure of 2-10. Figure 3-3 Crystal structures of [2-10 M]3+, M= Tm, Yb.

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84 Figure 3-4 Crystal structure of 2-13.

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85 CHAPTER 4 INTRODUCTION 4.1 Porphyrins Porphyrin is a heterocyclic macrocycle that consis ts of four pyrrole units linked by four methine bridges from their -carbons, as shown in Figure 4-1. The bridging methane carbons are called meso carbon atoms. The carbon atoms at the outer part of the pyrrole rings are called the -carbon atoms. Free base porphyrins and their metal analogues pl ay an important role in many biological processes, including absorption of sunlight and electron transf er for the initial step of photosynthesis91 and oxygen transport and storage taking place in hemoglobin.92 Porphyrins and their derivatives are also used as catalysts in industrial proces ses, and as photosensitizes in photodynamic therapy.93 They are important as organic semiconductors and nonlinear optical materials with their extended -electron systems.94 They also form an impo rtant class of aromatic dyes.95 Porphyrins have interesti ng spectroscopic properties96 which are affected by the type of the central metal atom, types of the substituents and their locations,97 and aromatic fusion of molecules to the porphyrin ring system. As a result the intere st in the experimental and theoretical studies on the UV-Vis spectra of porphyrins has been increasing. 4.2 Goutermans Four Orbital Model for the Spectroscopic Properties of Porphyrins The experimental near-UV-Vis absorption spec tra of porphyrins exhibit a weak absorption in the visible region at approximately 550 nm which is referred to as Q band.98 In addition; there is a very strong absorption band at around 400 nm in the near-UV region. This band is called the Soret band or the B band.98 Both the Q and B bands result from transitions96 and are explained by Goutermans theory with four orbital model.99 According to four orbital model,

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86 the Soret bands and the Q bands are taking place due to the transitions between the two top filled orbitals and the two lowest unoccupied orbitals of the porphyrins.99 As it is seen in Figure 4-2a, for the perfect D4h symmetry the two top filled orbitals, HOMO-1 and HOMO orbitals, are accidenta lly almost degenerate and have a1u and a2u symmetries, respectively. These two orbitals ha ve different electron pa rticipations and nodal structures.100 The meso -carbons of a2u orbital have high electron density but the electron participation on the -carbons is very low. The situation is the opposite for the a1u orbital. The participation on the -carbon atoms is very high and there is none on the meso carbon atoms.101 The two lowest unoccupied orbitals (LUMO) are degenerate and have eg symmetry. The excited state configurations of these orbitals, as shown in Figure 4-2b, are a1u 1eg 1 (HOMO-11eg 1) and a2u 1eg 1 (HOMO1eg 1). The symmetries of these transitions are Eu in D4h point group and these transitions have two equivalent dipole transitions in the x and y directions.99 These configurations are nearly degenerate and they generate a st rong configuration interaction (CI) which results in a high-energy state and a low energy-state.102 The high-energy state corresponds to the B-band and the low energy state corresponds to the Q band.102 Due to near degeneracy of these configurations, their contributi ons to Q and B bands are not equal.101 The lower energy configuration, a2u 1eg 1 (HOMO1 eg 1), has more contribution to th e Q band and the higher energy configuration a1u 1eg 1 (HOMO-11 eg 1) has more configuration to the B band101 which is depicted in Figure 4-2c. Generally, Qx, Qy, Bx and By are used as labels for the individual components of the transition pairs. Qx 0, Qy 0, Bx 0, and By 0 are the labels for the pu re electronic transitions. Qx 1, Qy 1, Bx 1, and By 1 are used for the vibronic overtone s of the electronic transitions.99 In case of free base porphyrin, x and y axes are not equivalent and as a result Qx and Qy bands are split.99

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87 Referring the pure electronic transitions of Q and B states of any porphyrin to Q0 and B0 states;99 2 / ) ( ) (1 2 2 1 0 0L H L H Q Bx x (4-1) 2 / ) ( ) (2 2 1 1 0 0L H L H Q By y (4-2) In equations (4-1) and (4-2), ( H1L2) defines singlet states for the transition H1 L2 etc. These states take place when H1, H2 and L1, L2 are degenerate.99 Among the states considered, Q0 gives the forbidden visible band, and B0 gives the allowed UV bands. Assuming the states of different polarization does not mix; it is proven by perturbation theo ry that for the Q states of any porphyrin, for each of the polarization, the visibl e band becomes allowed with the break down of the equality of the transition energies.99 When the free base formation is considered, th e energies of the orbitals change. If the hydrogens are attached to the second and forth pyr role nitrogens (Figure 4-1), then L2 will be lowered with respect to L1.99 It is harder to predict the situat ion for H1 and H2. As it is given in Figure 4-3, if H1 is lower in energy, then the energy of x polarized transitions will be close and the energy of the y polarized transitions will be different. As a result, Qy will be strong and Qx will be weak. In case of having H1 having hi gher energy and H2 having lower energy, the opposite trend will be observed.99 The energetic ordering, the spacing and the molecular orbital (MO) amplitudes of the orbitals of any porphyrin change depending on the substituents.101, 103 Electron withdrawing and electron donating groups determine th e stabilizations of the orbitals.101 While placing electronwithdrawing groups at the meso carbons or inserting a metal ion to the pyrrole nitrogens stabilizes a2u (H2) orbital, placing electr on-withdrawing groups on the -pyrrole carbons

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88 stabilizes a1u (H1) orbital.100 Thus prediction of the Q and the B bands depends totally on the stabilizations or destabilizations of the molecu lar orbitals with respect to the substituents. The transition dipoles of the individual transitions are combined by configuration mixing in such a way that B band has a strong intensity and Q band has a weak intensity.102 Most theoretical calcula tions are in good agreement with this model, although some studies comment on the necessity of accounting for more transitions involving lower occupied and higher unoccupied orbitals in addi tion to Gouterman model orbitals.104 4.3 Theory and Computational Chemistry 4.3.1 General aspects of Quantum Chemistry It is not possible to interpre t the spectroscopy, reactivity a nd the physical properties of a molecule without understanding the elec tron distribution in that molecule.105 Since classical mechanics can deal with only the macroscopic particles, for microsc opic particles quantum mechanics (wave mechanics) was developed.106 According to quantum mechanical approach to a system of N particles, all the properties of the system is in a wave function, This is a function of time and the coordinates of the N particles.105 The wave functions are th e eigen functions of the Hamiltonian operator and as a result the energies are the eigen values of the Hamiltonian operator.105 The wave function is required to be continuous (including its par tial derivatives), normalizable, and finite.106 Also the probability density represented by a particul ar wave function should be single-valued.106 In this way the eigen values of the operator will be meaningful for the properties of the chemical system. The wave function is time-dependent when tim e is included in the wave function. In order to see the future state of system from the knowledge of the pr esent state, there should be an equation that shows how the wave function changes with time.106 This concept was pointed out

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89 by Austrian physicist, Schrdinger. Since then, the equation is known as Schrdingers equation. The time-dependent Schrdinger equa tion is given in Equation 4-3.107 V m m t i2 2 2 2 1 1 21 1 2 (4-3) In this equation, 2 h where h is the Plancks constant, 1 i, m is the mass of the interacting particles, and V is the potential en ergy of the system. The equation has the first derivative of the wave function with respect to time and in this way future state of the system can be calculated if the wave function at time t0 is known.106 The system is in stationary state when time is not included in the wave function explicitly. Then the wave function is sa id to be time-independent wave function.105 Timeindependent Schrdinger equation can be written by using the Hamiltonian given in equation 4-4 assuming Born-Oppenheimer approximation.106 In this equation el ectrons and nuclei are assumed to be point masses and spin-orbit c oupling and other relativis tic effects have been neglected. jj i ij i i i ir e r e Z r e Z Z m m H2 2 2 2 2 2 22 1 2 (4-4) Here and present nuclei and i and j present elect rons. The first term in the equation is the kinetic energy operator for the nuclei, the s econd term is the kinetic energy operator for the electrons, the third term refers to the repulsions between the nuclei, r is the difference between nuclei and with atomic numbers Z and Z.106 The forth term refers to the attractions between the electrons and the nuclei in which ri is the distance betwee n electron i and nucleus The last term is the repulsion between the electrons and rij is the difference between electron i and electron j.106 Time independent Schrdinger equation is as follows:

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90 ) ,........, ( ) ,........, ( 1 1 n nr r E r r H (4-5) In this equation ir is the position of the ith electron and N is the total number of electrons present in the system. E represents th e total electronic en ergy of the system.106 The main purpose of solving Schrdinger equation is to find the coordinates of atoms of the molecule that gives the minimum energy value, E0. However, it is very hard to solve the entire equation. The reason for the Schrdinger equation to be so complicated is that it consists of 3N electron Cartesian coordinates, N electron spin coordinate s and 3N nuclear cartesian coordinates.106 In order to simplify the calculation of the Schrdinger equa tion, variation method is applied to the Schrdinger equation. In this way an approximation is applied to the equation for the ground state energy of the system.106 The main advantage of variation me thod is that it he lps to calculate an upper bound for the ground state energy.106 The variational principle is defined by Equation 46: d d H *E0 (4-6) In this equation, is the trial function, ad E0 is the ground state energy. The lowest value of the integral gives the closest value of the energy the ground state energy. Computation of accurate self-consistent-fie ld (SCF) wave functions is an important development in computational chemistry.106 The wave function is written in terms of antisymmetrized product of spin-o rbitals. Each spin orbital is a product of a spatial orbital and a spin function; either or .106 These spatial orbitals minimize the variational integral. They are calculated by solving the Hartree-Fock equations.106 given in equation 4-7. ) 1 ( ) 1 ( ) 1 (i i i effH (4-7) In this equation i is the orbital energy. The effectiv e Hartree-Fock Hamiltonian operator is as shown in equation 4-8.

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91 j j j effK j r Z H ) 1 ( ) 1 ( 2 2 1 ) 1 (1 2 1 (4-8) The first term is the kinetic energy term for one electron and the second term is the potential-energy operator taking into account the attraction between one electron and the nuclei.106 Here jJ is the Coulomb operator and jKis the exchange operator106 which are depicted in equation 4-9 and 4-10, respectively. 2 12 21 ) 2 ( ) 1 ( ) 1 ( ) 1 ( dv r Jj i i j (4-9) 2 12 *) 2 ( ) 2 ( ) 1 ( ) 1 ( ) 1 ( d r Ki j j i j (4-10) The Coulomb operator defines the potential en ergy of interaction between one electron and the second electron with electronic density 2) 2 (j The factor 2 comes from the fact that there are two electrons in each spatial orbital.106 The exchange operator does not have physical interpretation but comes from the fact that th e wave function needs to be antisymmetric with respect to electron exchange.106 4.3.2 Basis Sets Hartree-Fock calculation is the calculati on for which SCF uses antisymmetrized spin orbitals. Hartree-Fock orbitals can be written linear combinations of a complete set of known functions, basis functions.106 The orbitals that are being used during calculations should be defining the shielding effects if the other electrons in the system, as a result they should follow certain rules for the effective atomic number.108 One of the most commonly used set of orbitals are Slater type orbitals (STO). In equation 4-11 the equation of STOs in polar coordinates are given. n, l, m (r, )= NYl,m( )rn-1er (4-11)

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92 In this equation n is the principle quantum number, l is the angular momentum quantum number and m is the magnetic quantum number; Yl,m is a spherical harmonic.108 N is the normalization constant in th e equation and the parameter is defines as orbital exponent.106 In order to make calculations simpler, anot her type of orbitals were proposed called Gaussian type orbitals (GTO). In equation 4-12, the equation of GT O is given in polar coordinates.106 n, l,m (r, )= NYl,m ( )rl 2. re (4-12) As in Stops, N is the normalization factor, Yl,m is the spherical harmonic and is the orbital exponent. Unlike STOs with an exponential factor of exp(r), GTOs have an exponential factor of exp(r2).106 For smaller numbers of r, the Gaussian function defines the atomic orbital in a poor way because Gaussian functions do not have cusp when r is small. In order to overcome this deficiency, linear combinations of se veral Gaussians are used to define an atomic orbital as a result of which the number of integrals used in SCF calculation with GTOs is more than that of STOs.106 In spite of this fact, calculations with GTOs take less time than STOs because the product of two Gaussian functions at two certain point s gives a single Gaussian at the third point.106 When the basis functions are considered, each molecular orbital is defined as a linear combination of one-electron or bitals centered on each atom.106 SCF calculations can be carried out by two different methods: Methods that use mi nimal basis set or methods that use extended basis set of atomic orbitals.106 A minimal basis set contains onl y inner shell and valence shell atomic orbitals. An extended basis set uses inne r shell and valence shell atomic orbitals in addition to higher shell atomic orbitals.106 Minimal basis set calculations are easy but extended basis set calculations are more accurate.106

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93 4.3.3 Density Functional Theory 4.3.3.1 Hohenberg-Kohn theorems When the Schrdinger equation is considered that is discussed previously, for an N electron system, 3N coordinates are taken into account during calculations and due to electronelectron interactions the equation can not be reduced into simpler form.109 One-electron density matrix, given in equa tion 4-13, or the two electron density matrix, as in equation 4-14, describe most experimental observables.109 N N nr d r d r d r r r r r r r r N r r ... ) ,....., ( ) ,....., ( ) (3 2 3 2 3 2 ) 1 ( (4-13) N N Nr d r d r r r r r r r r N N r r r r ... ) '...., ( ) ,...., ( 2 ) 1 ( (3 3 2 1 3 2 1 2 1 2 1 ) 2 ( (4-14) The electron density in position sp ace is defined in equation 4-15. ) ( ) () 1 (r r r (4-15) According to Hohenberg and Kohn, the electron density) ( r of the ground state defines the external potential Vext( r ) so the electron density in three-dimensional space is enough to write the full Hamiltonian operator which will lead to the solution of the Schrdinger equation.109 Therefore any ground state property can be determined and any ground state property is considered to be a functional of ) ( r .109 There is an important thing to be indicated at this point. This theorem is a theorem that proves the existence of the functionals but the theorem does not explain how to obtain these functionals.109 The total electronic energy (E) is a ground stat e property and it is de fined as a functional of electron density with resp ect to Hohenberg-Kohn theorem.109 This relation is given in equation 4-16. E=E[ ] (4-16) Also total number of electrons (N) are considered to a functional of .109 This relation is given in equation 4-17.

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94 N= r d r ) ( (4-17) Another relation that was pr oved by Hohenberg and Kohn is that any trial density obeying equation 4-17 also obeys the following equation, 4-18.109 E E ~ (4-18) The relation given in equation 4-18 indicated that Hohenberg-Kohn theorems consider the calculation of the total electronic energy whenever variational principle is applied.109 4.3.3.2 Kohn-Sham equations The total kinetic energy of the system is considered to be a ground state property and it is a kinetic energy functional of electron density,109 as seen in equation 4-19. T=T[ ] (4-19) It is also possible to write the external potential and the cla ssical Coulomb energy (Vc) as a function of density.109 They are given in equations 4-20 and 4-21, respectively. r d r V rext ) ( ) ( (4-20) r d r r V r d r d r r r r ec ) ( ) ( 2 1 ) ( ) ( 22 1 2 1 2 1 2 (4-21) The total energy y functional, E[ ], can be written as follows; ] [ ) ( 2 1 ) ( ) ( ] [ ] [ xc c extr d r V r V r T E (4-22) The term with [ ] is called as the exchange-correlati on energy functional and it contains all the non-classical interactions.109 When variational principle is applied including the relation given in 4-20, via langrange multiplier, following equation is achieved; XC c extr V r V T N r d r E ) ( ) ( 0 ) ( (4-23) This equation was compared with the one obtained that had N interacting particles moving in another ex ternal potential Veff, the total density of both systems were determined to be

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95 equal.109 As a result, equation 424 was achieved in which ] [ ~ T represents the kinetic energy of the non interacting particles. ) ( ~ r V Teff (4-24) The Schrdinger equation fo r N particles can be solved easily because it can be separated into N equations in the following way;109 ) ( ) ( ) ( 22 2r r r V mi i i eff (4-25) And the total density of these N particles is given by equation 4-26. 2 1) ( ) (N i ir r (4-26) When equations 4-23 and 4-24 are compared following equations are derived;109 ) ( ) ( ) ( ) ( ) ( ~ ) ( ) ( ) ( r V r V r V E r V r V T T r V r V r VXC c ext XC C ext XC c ext eff (4-27) According to this equation; XC XCE r V ) ( and T T EXC XC ~ (4-28) The total energy of the N individual elect rons is basically sum of their indivi dual energies but it is not the same for the real system.109 The total energy of the real system is given in equation 4-29. ] [ ) ( 2 1 ) ( ) ( 2 ] [1 1 2 2 1 XC C ext N iE r d r V r V r m E (4-29) This equation can also be written as; ] [ ) ( ) ( 2 1 ) ( ] [1 xc XC C N i iE r d r V r V r E (4-30) VXC and EXC are electron density () ( r ) functionals and their relation with electron density is seen in Equation 4-28. VXC is defined as a function of three-dimensional position

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96 coordinate but it is also dependent on the behavior of electron density, () ( r ) .109 The precise form of VXC is not known.109 During calculations of a system homogenous el ectron gas is considered. This approach builds a simple system with accurate quantum mechanical calculations.109 However, for some systems in which electron distribution is not homogenous, local-d ensity approximation (LDA) is used.109 In this approximation VXC which is a function of the position coordinate r is calculated at point r to find out what it would be at that point if it were homogeneous electron gas at that point.109 This approximation neglects the effects dues to variations in electron density, ) (r On the other hand, this approach s parameter-free.109 Since during calculations for the properties of the system integrals over all the space are taken into account, some errors are averaged out.109 In some cases LDA calculations are not e fficient for accurate results so non-local functionals are improved which are the functionals of and 2as well as .109 In order to achieve better re sults, there have been attempts to combine Hartree-Fock and DFT methodologies to make hybrid methods.109 among these attempts; the most successful one is with Beckes three parameter exchange f unctional with Lee, Ya ng Parr (LYP) correlation effects. There have been accurate results with these functionals but calculations become more extended since the number of paramete rs increase with these functionals.109 The advantage of these approximate functionals is that they are pa rameter-free and they are general for all systems, atom types and structures.109 4.3.4 Electronic Spectroscopy When thee electric field component of radiat ion interacts with a molecular system, the radiation is absorbed by the molecule.105 The absorption takes place wh en the radiation matches

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97 the energy difference between the quantized energy levels of different states of the molecule.105 This change in the electronic state of the molecu le takes place when an electron in the bonding or nonbonding molecular orbital of the molecule in its ground state is excited into an empty molecular orbital at higher energy.105 The Morse potential in Figure 4-4 shows the transitions for absorption and emission between the electronic ground and excited states.105 There are different methods to calculate th e electronic transitions of the molecules. Configuration interac tion is a common method among all these methods. Wave functions defining only single configuration are not true wave functions of the Hamiltonian operator since they do not contain electron correlation.110 The correlation is the contri bution of the higher states to the state of interest with comparable symmetry.110 By the mixing of different excited state configurations, the wave function converges into the true wave function.110 Another method for the calculation of excite d states is the time dependent density functional theory (TDDFT). A ccording to the central theorem of TDDFT (Runge-Gross theorem), there is a one-to-one corresponde nce between time-dependent potential, ) (t r Vext and the electronic density,) ( t r .111 As a result, if the density of a system is known, the external potential can be calculated. In this way Schrdinger equation can be solved.111 It is important to know the initial state of the system. In order to construct a time dependent KohnSham scheme, noninter acting electrons under external local potential KSV.111 This potential is chosen in a way that the density of the noninteracting orbitals and the density of Kohn-Sham electro ns are the same.111 The Kohn-Sham electrons follow the time-dependent Sc hrdinger equation given in equation 4-31. ) ( ) ( ) ( t r t r H t r t ii KS i (4-31) Kohn-Sham Hamiltonian is given as follows;

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98 ) ( 2 ) (2t r V t r HKS (4-32) To be able to calculate the density of th e interacting system from the calculated KohnSham orbitals,111 equation 4-33 is used. 2) ( ) (N it r t r (4-33) The time dependent Kohn-Sham potentia l is depicted in equation 4-34. ) ( ) ( ) ( ) ( t r V t r V t r V t r VXC Hartree ext KS (4-34) The first term in equation 4-34 is the exte rnal potential, and the second term is the electrostatic repulsion term between the el ectrons which is given in equation 4-35.111 ) ( ) (3r r t r d t r VHartree (4-35) The last term in equation 4-34 is the XC potential that contai ns nontrivial many-body effects.111 It has an unknown functional dependent on the density both in space and in time.111 It is important to make a careful approximation fo r XC potential because the quality of the results are related to the approximation made for this potential.111 This is the only major approximation in TDDFT like that of in ground-state DFT.111

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99 HN N NH N Figure 4-1 Structure of porphyrin. N N N N N N N N N N N N N N N N a2u H2 a1u H1 eg L1 eg L2Ene r gyLUMO HOMO (a2u) (eg) yy H1 H2 L1 L2 HOMO-1 (a1u) xx Figure 4-2 Goutermans four orbital model for a D4h porphyrin. A) Schematic representations of electron densities for the two HOMO and tw o LUMO orbitals. B) Mixing of four allowed transitions within the four orbitals via configuration interaction (CI). C) The absorption spectrum of porphyrin and the contributions of higher energy configuration, a1u 1 eg1, to the B band and the lower energy configuration to the Q band. meso -carbon ato m 4 3 2 1 -carbon atom A B C

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100 L1 L1 x x x x y y y y H1 H2 Figure 4-3 Possible transitions am ong the four orbitals of the porphyrins with the change of ordering of the orbitals. Figure 4-4 The transitions for absorption and em ission between the ground and excited states.105 L2 H2 L2 H1

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101 CHAPTER 5 COMPUTATIONAL CALCULATIONS FOR CIS -AZULENEONE AND TRANS AZULENEONE 5.1 Computational Approach to Porphyrins and Porphyrin Derivatives The interesting spectroscopic properties of porphyrins have attracted computational chemists to work on these molecules. Computat ional studies with diffe rent calculation methods, semiempirical111, 112, Hartree-Fock (HF)113, 114, post-Hartree-Fock115, 116 (methods that are developed to improve HF), and De nsity Functional Theory (DFT),117, 118 have been applied to different porphyrin derivatives and the efficiency of these methods have been compared with respect to each other.96 In these studies post Hartree-Fock me thods turned out to be very costly. DFT method has become the most comm on method for porphyrin type molecules91, 92, 101, 118-124 because, unlike ab initio and/or semi empirical HF methods it takes into account electron correlations125 that are necessary for porphyrin type mo lecules. Therefore it is more successful and more reliable for the geometry optimizations and energy differences between the electronic states of these molecules in terms of being consiste nt with the experimental results. Studies also revealed that using higher level of theory rather than using la rger basis set gave much better results.126 For the excited state calculati ons the most reliable method was determined to be time dependent density functional theory (TDDFT) over single excitation conf iguration interaction (CIS or CI-Singles) calculations.93, 127, 128 It is being used for porphyrin systems95, 129 because only TDDFT is able to provide extensive configuration mixings that characterize the excited states of porphyrins and their derivatives.102 Although many studies have been done with the porphyrin derivatives, molecular orbital studies for the expanded porphyrin systems, porphyr ins containing fused aromatic units, are very rare. These porphyrin systems show interesting spectroscopic charac teristics because they shift

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102 the absorptions to lower energies or they lower th e symmetry of the molecule so that degenerate transitions are split.130 Keeping these facts in mind we were interest ed in two different isomers of exceedingly large free base porphyrins, cisAzuleneone, 5-1a, and transAzuleneone, 5-2a, reported previously, bearing bis(napht hoazuleneone) ring systems,131 as depicted in Figure 5-1. According to electronic absorption spectra of these molecule s, the Q bands of both of the isomers were red shifted to near-IR region.131 The trans isomer was more red shifted than its cis analogue.131 Electrochemical data for cisAzuleneone was consistent with the spectroscopic data for the lowest energy absorption. In order to understand the experimental behaviors of these two expanded porphyrin systems, we performed DFT calculati ons on the simplified derivatives of 5-1a and 5-2a. These simplified derivatives, 5-1b and 5-2b, were created by replacing the mesityl and tert-butyl groups on the molecules by hydrogens to make th e computational calculations easier. The structures of 5-1a, 5-2a, and optimized structures of their simplified derivatives 5-1b and 5-2b are given in Figure 5-1. TDDFT was applied for the excited stat e calculations. Experimental and computational data were compared and the resu lts were predicted depending on the calculated molecular orbitals. 5.2 Computational Methods The structures of 5-1b and 5-2b were created by Hyperchem 7133 program and were optimized by density functional theory by usin g Beckes three parameter hybrid functional134, 135 combined with Lee-Yang-Parr136 correlation functional, B3LYP, with 6-31G basis set by using the Gaussian 98137 program. Symmetry constraints were ap plied to the optimized structures of the molecules in order to achieve the desired poi nt groups. The structures were verified to be minima by frequency calculations with the same basis set. Single point calculations for Kohn-

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103 Sham orbitals were carried out with 6-31G* basi s set. TDDFT calculations for the excited states were performed with the same basi s set used for the single point calculations. All the calculations were performed by high performance computers at QTP at University of Florida. During the calculations Xena II system was used which is co nsidered as high perfor mance cluster to solve computational problems under Xena Cluster Project at Quantum Theo ry Project at University of Florida. This system has 192 nodes. Each of these nodes has a 135 MHz POWER2SC CPU, 1 GB of RAM and 9 GB of disk space.138 The nodes are connected by a redundant path SP switch with a 150 MB/sec rate. The global storage of the system is 420 GB. It has 192 2.2 Gb disks on 16 SSA adapters. These adapters are connected to each node as a general parallel file system (GPFS) through the SP switch.138

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104 N N O N N O H R H H R H H R H H R H H A r H H H A r N N O N N O H H H H H H H H H H H H H H H H H H 5-1a 5-1b (Cs) A N N N N H Ar H H H O O H R H H R H R H H R H H Ar N N N N H H H H H H O O H H H H HH H H H H H H 5-2a 5-2b (C2h) B R = t-Bu Ar = Figure 5-1 Schematic representation of A) cis Azuleneone, 5-1a, and its simplified derivative 51b created for the calculations B) transAzuleneone, 5-2a, and its simplified derivative 5-2b used in the calculations.

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105 CHAPTER 6 MOLECULAR ORBITAL APPROACH FOR TH E ELECTRONIC EXCITED STATES OF CIS -AND TRANS -AZULENEONE 6.1 Molecular Structures All the calculations for 5-1b and 5-2b were performed with totally theoretical approach without using any experimental data for the ini tial coordinates of the molecules. These planar molecules are defined as cis and transisomers of each other due to the positions of oxygens in the structures. The symmetry point groups of 5-1b and 5-2b are Cs and C2h, respectively, as depicted in Figure 5-1. In Figure 6-1 the crystal structure of 5-1a is shown. For simplicity hydrogen atoms have been removed from the structure. Crystal structure of 5-2a is not available. Experimental bond lengths () for 5-1a and calculated bond lengths () for 5-1b are given in Figure 6-2 and Figure 6-3, resp ectively. Hydrogen atoms have been removed from both of the structures. The molecule is symm etric in solid state bearing a C2 axis so all the bond lengths are being symmetrical for the experimental data. When the calculated and experimental bond lengths for the cis isomer are compared, it is seen that there is a good agreement between the values. The differences between the bond lengths are smaller than 0.027 except for the oxygen-carbon bond lengths. The mean absolute deviation, |d |, for the calculated and so lid state bond lengths is 0.011 The deviations between the experimental and calculated bond lengths are less than 2% error. For the case of oxygens there is a higher deviation. The difference betw een the calculated and experimental bond length for the carbonyl oxygen is 0.036 which is around 2.85 % error. From these values it can be concluded that there is a good correlation betwee n the experimental and calculated bond lengths. Since there is no crystallographic data for 5-2a, only the calculated bond lengths are presented in Figure 6-4.

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106 Calculated bond lengths for the trans isomer are very similar to those of cis isomer. This is expected since the substituents on each side of the porphyrin co re are the same. Both of the molecules are highly conjugated -systems containing double and single bonds and the calculated bond distances are in the expected interval fo r the single and double bond lengths. In addition to bond lengths, calculated bond angl es are also in good agreement with the experimental data for 5-1b. Selected calculated and experiment al angles inside the porphyrin core for 5-1b are given in Table 6-1. Numbering scheme for the carbon atoms are given in Figure 6-5 for the cis isomer. The carbon atoms are labeled according to standard numbering for the porphyrin core. For clarity, hydrogen atoms are removed. Table 6-1. Selected experimental and calculate d angles on the porphyrin core for 5-1a and 5-1b. Angle 5-1a 5-1b C20C1N1 125.8 125.2 N1C4C5 122.9 123.6 C4C5C6 124.9 125.0 C5C6N2 135.1 136.2 N2C9C10 122.2 121.6 C9C10C11 121.0 123.0 C10C11N3 122.2 120.1 N3C14C15 135.1 138.4 C14C15C20 124.9 124.8 C15C16N4 122.9 122.2 N4C19C20 125.8 125.0 6.2 Calculated Orbitals and the Spectra for the cis and trans Derivatives of Azuleneone When the experimental and calculated spectra are compared there is a good agreement between them. The Q band of the porphyrin is at 500 nm-600 nm region.139 The lowest energy band for the 5-1a is not around 600 nm but at 923 nm expe rimentally. There are two calculated transitions for 5-1b, 11A' and 21A' at 1032.55 nm, and 915.83 nm, wh ich are contributing to the band in the experimental spectrum at the low energy region that has a maximum peak value at

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107 923 nm. These calculated transitions are the split Q1 and Q2 bands respectively as depicted in Figure 6-6. For the transAzuleneone the lowest energy band is at 1100 nm experimentally. On the calculated spectrum for the singlet states of 5-2b, this low energy is calculated to be at 1049.77 nm with 11Bu symmetry. This Q band transition is main ly from HOMO to LUMO orbital. There is a small contribution coming from HOMO-2 orbital for this transi tion as shown in Figure 6-7. It is both experimentally and theoretically proved that both of the molecules are red shifted, trans -Azuleneone being more red shifted than its cis isomer. It is clearly seen from the Kohn Sham molecular orbital di agrams. The HOMO-LUMO energy ga ps for these molecules are calculated to be close to each ot her. The HOMO-LUMO gap for the cis isomer is slightly higher than the trans isomer. More red shifted trans -isomer has its lowest energy tr ansition with 76.60 % weight coming from HOMO-LUMO interaction. On the othe r hand the lowest energy transition for the cis isomer is 59.80% with HOMO-1-LUMO and 29.40% HOMO-LUMO interaction which makes this transition relatively higher in energy. These molecules are red shifted because -conjugation provided by the substituents on the rings decrease the HOMO-LUMO energy gap with the electronic effects to the original porphyrin ring. Detailed analysis of the four frontier orbitals shows these electronic effects depending on the electron distributions. There ha ve been several porphyrin systems reported in the literature for the effects of the substituents for the red shift of the Q bands.94, 97, 98, 131, 140, 141144

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108 In the literature it is also reported that w ith the increase of the size of the molecular structure, Q band becomes more pure.131 This is also observed in our large molecules. All these important results are discussed in detail in the following sections. 6.2.1 Kohn-Sham Orbitals The energy levels of the orbitals of a porphyrin derivative are determined by the substituents. The symmetry of the molecule with the substituents is responsible for the redistribution of orbital coefficients.103 The ordering and the ener gy differences among the molecular orbitals in addition to the strength of the configuration inter action coupling affect the interaction of the four porphyrin orbitals.101 The Kohn Sham orbital di agram of some frontier orbitals and the isoamplitude surfaces of their wave functions for both of the molecules are shown in Figure 6-8 and Figure 6-9, respectively. Energies of some of the calculated frontier molecular orbitals (MOs) are presented in Table 6-2. Regarding the electronic transitions taking pl ace for the UV-Vis spectra of the molecules, the energy levels of the HOMO-1, HOMO, LUMO and LUMO+1 orbitals and the differences of the energies between these orbitals have strong relevance for the interp retation of the spectra. Due to the lowering of symmetry, LUMO a nd LUMO+1 orbitals are not degenerate.99 The energy differences of the LUMO and LU MO+1 orbitals are 0.735 eV for the cis and 0.655 eV for the trans isomer. It is clearly seen that the ener gies of LUMO and the LUMO+1 orbitals and the LUMO-LUMO+1 energy differences of the two molecules are not very different from each other. On the other hand, the energy diffe rences of HOMO and HOM O-1 orbitals of the molecules are not as close to each other. The HOMO-HOMO-1 energy differences for the cis and trans isomers are 0.121 eV and 0.688 eV, resp ectively. The HOMO-LUMO gaps were calculated to be 1.664 eV for 5-1b and 1.592 eV for 5-2b. These values indicate that the HOMO-

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109 LUMO energy differences of the two molecules are very close to each other. The slight difference of HOMO-LUMO gap and the fact that the trans isomer has the smaller HOMOLUMO gap support both the calculated and the expe rimental electronic abso rption spectra of the molecules. The lowest energy transition for the trans isomer, both on experimental and calculated spectra, is lower than the one for the cis isomer which means that trans isomer is red shifted more than the cis isomer. This can easily be seen in Figure 6-6 and Figure 6-7 which show the calculated oscillator strengths plotte d as a function of tran sition wavelength and the experimental spectra being overlai d on the same plot for each of 5-1b and 5-2b, respectively. Table 6-2. Calculated Molecular Orbitals Symmetries and Energies (eV) for 5-1b and 5-2b. 5-1b 5-2b MO Symmetry Energy (eV) Symmetry Energy (eV) LUMO+4 a -1.101 au -1.038 LUMO+3 a -1.575 bg -1.529 LUMO+2 a -2.593 au -2.593 LUMO+1 a -2.727 bg -2.809 LUMO a -3.462 bg -3.464 HOMO a -5.126 au -5.056 HOMO-1 a -5.247 au -5.744 HOMO-2 a -6.104 bg -5.779 HOMO-3 a -6.310 au -6.328 HOMO-4 a -6.561 ag -6.602 Electron delocalizations on the orbitals are important for the interpretations of the transitions in the excited state. In case of LUMO +1 orbitals, as seen in Figure 6-9, electrons are localized on the porphyrin core for both the cis and trans isomers. The cis isomer has very small participation of electrons on the phenyl groups which is a very slight difference from the

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110 LUMO+1 orbital of the trans isomer. Unlike LUMO orbitals, unsubstituted meso carbon atoms have high participation and substituted meso carbon atoms have no participation. When -carbon atoms are considered, there are high orbital amp litudes in each of the molecule. The nitrogen atoms, however, have less amplitude when compar ed to LUMO orbitals. The main difference for the LUMO+1 orbital of the cis isomer is that if we assume th ere is a hypothetical plane passing through the substituted meso carbon atoms dividing the molecule into two halves as upper half with both oxygen atoms and lower half without any oxygen atom, the participation for the porphyrin ring in the upper half ar e higher than those in the lower half of the molecule. For the trans isomer, since the oxygen atom s are located in a more symmetrical way, one in the upper half and one in the lower part the amplitudes on the porphyrin ring are not different from each other for different halves of the molecule. It is clear that location of the oxygens affect the electron localizations in LUMO+1 orbitals. When LUMO orbitals are comp ared, there is an electron de localization over the entire molecule for each of the system. The amplitudes and the pattern of electron delocalizations on the phenyl rings, seven membered rings, and on th e porphyrin core are very similar for both of the isomers. There is a nodal plane passing through the unsubstituted meso carbon atoms observed for both of the LUMOs. On the other hand the amplitudes for the substituted meso carbon atoms, -carbon atoms and the nitrogen atoms are high for each of the isomer. Considering HOMO orbitals, electrons are de localized over the entire molecules in a similar manner for the substituents and the porph yrin cores for both of the molecules. Both molecules have high amplitudes on all of their meso carbon atoms and nitrogen atoms. Relatively small participation on the phenyl rings on one side of the cis isomer brings the difference of the electron distribution on the HOMO orbita l when compared to that of the trans isomer. Electron

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111 distribution for HOMO orbital of trans isomer is more homogenous than its cis analogue. This must be due to higher symmetry of the trans isomer. The biggest difference is observed with the HOMO-1 orbitals of the isomers. Electron distribution for 5-1b is in such a way that, the part of the molecule that had only small amplitudes for HOMO orbital now has high elect ron contribution for the case of HOMO-1 orbital. Similarly, the part of the molecule that had high amplitude now has very small amplitude. The substituted meso carbon atoms have no electron distributions. Similarly the participations on the substituted meso carbons for the trans molecule are very small, almost negligible. The amplitudes on nitrogen atoms on HOMO-1 for 5-2b are much smaller when compared to HOMO orbital of this molecule. HOMO-1 orbital of 5-2b shows electron delocalization over the entire molecule, unlike 5-1b. Due to better distribution of the electrons, distribution over a higher number of atoms, the stability of the bonds are improved145 and the HOMO-1 orbital for 5-2b is more stabilized when compared to HOMO-1 orbital of 5-1b. HOMO orbitals are more destabilized than HOMO-1 orbital since at the meso positions for the HOMO orbitals, where the substitution is taking place; there are high amplitudes at meso carbon. For the HOMO-1 orbitals these pos itions have very small amplitudes.97 According to Goutermans theorem99, 141 HOMO orbitals are accidentally degenerate with a1u and a2u symmetries. The a1u orbital has no amplitude at meso positions. It has very small participation at the -carbons. In case of a2u orbital there ar e high amplitudes on meso carbons and on nitrogens. Therefore these molecules are susceptible for energy changes depending on the substituents. The diagrams of HOMO orbitals reveal that fo r each isomer the porphyrin core keeps its a2u type character with high amplitudes at both the nitrogen atoms and meso carbon atoms. On the other hand, especially for the trans isomer, HOMO-1 orbital keeps its a1u type character.

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112 Destabilization of the a2u type orbital, (hi gh participations at meso positions) with respect to a1u type of orbital (small participations at -carbon atoms) for the porphyrin core is expected,103, 131, 140, 146 since aromatic rings are fused into the porphyrin system through alternating meso positions. Although alternating -carbon atoms are also involved in substitution, due to their low orbital participations, they would not make significant change for a1u. 6.2.2 Excited States In order to be able to interpret the ex perimental spectra for both cisand transAzuleneones, excited state calcul ations were carried out by TDDF T for the first fifteen singlet excited states of 5-1b and 5-2b. The calculated osci llator strengths were plotted as a function of transition wavelength for 5-1b and 5-2b are presente d in Figure 6-6 and Figure 6-7, respectively, as stated before. Experimental spectra of the molecules are overlaid on the same plots. Calculated excited states with related symmetries, the weights of the transitions that have more than 2% contributions to the excitations, transiti on energies and oscillator strengths for the cis and trans isomers are given in Table 6-3. 6.2.2.1 Q-band regions for cisAzuleneone and transAzuleneone There is a good correlation between the experimental spectrum of 5-1a and calculated transitions of 5-1b. The two calculated singlet transitions at 1032.55 nm, and 915.83 nm with the symmetries 11A' and 21A', respectively, are c ontributing to the band at the low energy region with the maximum peak value at 923 nm for 5-1b. These calculated transitions are split Q1 and Q2 bands, respectively. In order to verify this interpretation, Gaussian broadening was applied to the calculated spectrum until the sum of the individual Gaussian component peaks was in good agreement with the experimental spectrum.104,

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113 147 Figure 6-10 and Figure 6-11 show the Gaussian br oadening curves with the actual spectra overlaid for 5-1b and 5-2b, respectively. It was clearly seen from the Gaussian broadening Table 6-3. Calculated electronic excited states, orbital configurationsa, b (% Weight), transition energies and oscillator strengths for th e first fifteen singlet states for 5-1b and 5-2b. 5-1b 5-2b (nm) Oscillator Strength (f) Energy (eV) Exc.St ate Orbital Contributionb (Weight %) (nm) Oscillator strength (f) Energy (eV) Exc. State Orbital Contributionb (Weight %) 1032..55 0.0109 1.2007 11A' H-1->L (59.80) H ->L (29.40) 1049.77 0.0881 1.1811 11Bu H >L(76.60) H-2 ->L+1(6.18) 915.83 0.1161 1.3538 21A' H-1 >L(28.40) H ->L (43.60) H-1->L+2 (6.40) H-1 ->L+1(4.80) H->L+1 (4.44) 710.49 0.0008 1.7450 21Bu H ->L+1 (53.80) H-2 ->L (46.80) 634.12 0.0266 1.9552 31A' H ->L+1 (55.20) H-2 ->L (23.74) H->L+3 (9.00) H-1->L+3 (6.04) 704.71 0.0000 1.7593 11Ag H-1 ->L ( 80.40) H ->L+2 (7.16) 608.38 0.0042 2.0379 41A' H->L+2 (51.40) H-1>L+1(32.40) H->L+1 (4.38) H-1->L+2 (3.72) 616.33 0.0000 2.0117 21Ag H ->L+2 (86.20) H-1 ->L (10.68) 584.45 0.0133 2.1214 51A' H-1 >L+1(31.60) H->L+2 (28.20) H-1 >L+2(20.66) H-2 ->L+1(6.76) H-3->L+1 (4.52) H ->L+1 (3.66) 580.01 0.1943 2.1376 31Bu H-2->L (25.40) H->L+1 (20.28) H-3 ->L(18.08) H-2 ->L+1(15.86) H-8 ->L(3.24) 533.86 0.2326 2.3224 61A' H-1 >L+2(44.60) H-3->L (32.40) H-1 ->L+1(4.10) H-2->L (3.36) H ->L+2 (2.28) 503.37 0.4747 2.4631 41Bu H-3 ->L(51.80) H-2 ->L+1(13.20) H-2->L (9.20) H ->L+1(6.80) H-8 ->L(2.98) 505.30 0.0000 2.4536 11A" H-5 ->L (83.00) H-5 ->L+1(6.88) H-5 ->L+2(5.38) 501.87 0.0000 2.4704 31Ag H-1 ->L+1(88.80) H-6 ->L(4.06) 502.69 0.2349 2.4664 71A' H-3 ->L (42.00) H-2 ->L (11.18) H-1 >L+1(10.48) H-7 ->L (10.30) H-2 ->L+1(4.34) 501.21 0.0000 2.4737 11Bg H-4 ->L(84.18) H-5 ->L+2 (9.20) 496.70 0.3321 2.4961 81A' H-2 ->L (37.74) H ->L+2 (16.58) H-1->L+2 (5.12) H-3 ->L (4.64) H-2 ->L+1(4.20) 499.09 0.0000 2.4842 1Au H-5 ->L(83.40) H-4 ->L+2(9.70) 460.40 0.1156 2.6930 91A' H-4 ->L (4.60) H-3->L+1 (2.40) 469.69 0.0000 2.6397 41Ag H-6 ->L(38.18) H-2->L+2(36.18) H-7->L(16.74) 453.03 0.0000 2.7368 21A" H-8>L+1(78.80) H-8->L+2 (6.68) H-8->L+1 (6.60) 457.70 0.0866 2.7088 51Bu H-1->L+2(51.40) H-2 ->L+1(24.00) H-3->L (10.66) H->H+3(5.26) 447.58 0.1253 2.7701 101A' H-7 ->L (47.60) H-6 ->L (28.88) H-4 ->L (4.10) 445.37 0.0000 2.7838 51Ag H-4->L+2(53.60) H-6 ->L(22.60) H-7 ->L(13.54)

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114 Table 6-3. Continued 5-1b 5-2b (nm) Oscillator Strength (f) Energy (eV) Exc.St ate Orbital Contributionb (Weight %) (nm) Oscillator strength (f) Energy (eV) Exc. State Orbital Contributionb (Weight %) 442.32 0.1072 2.8030 111A' H-6 ->L (59.20) H-7 ->L (26.12) H-2 ->L+1(4.86) 440.44 0.0583 2.8150 61Bu H-8 ->L(71.20) H-11 ->L(7.90) H-3 ->L+1(5.56) 414.41 0.0515 2.9918 121A' H->L+3 (60.34) H-2>L+1(28.60) H-2->L+2 (4.68) 440.42 0.0000 2.8151 61Ag H-7 ->L(62.14) H-6 ->L(26.40) 400.43 0.0251 3.0962 131A' H-3 >L+1(66.00) H-1 >L+3(15.18) H-2 ->L+2(5.84) 431.20 0.0172 2.8753 71Bu H-9 ->L(50.14) H-1 ->L+2(15.00) H ->L+3(11.40) H-8 ->L(5.36) H-2 ->L+1(5.14) a HOMO-1, HOMO, LUMO and LUMO+1 orbitals are re presented as H-1, H, L and L-1 respectively. b Configurations which contribute more than 2 % are shown. analysis that these peaks do not resolve in the sp ectrum, instead add up and together contribute to a broad peak. Therefore it is clear that these p eaks are contributing to the absorption peak in the experimental spectrum at 923 nm The calculated splitting energy, Q/cm-1, for Q1 and Q2 bands is 1234.3. For the symmetrically ring expanded porphyrin metal free species it was reported that for the split Q bands, the intensity of the one in the lower energy is lower than the one in the higher energy.131It is the case for 5-1b as can be seen from Table 6-3. The calculated intensity of higher energy Q2 band is 0.1161 and that of lower energy Q1 band is 0.0109. The intensity ratio for Q2/Q1 is 10.65. Considering the orbital contributions for 11A and 21A, it is seen that both of the transitions are mainly from HOMO-1 and HOMO orbitals to LUMO orbital. There are also small contributions for 21A state coming from HOMO-1 to LUMO+1, HOMO-1 to LUMO+2 and HOMO to LUMO+1 transitions. Electronic transition for 11A is the linear combination of two configurations from HOMO-1 to LUMO and HO MO to LUMO orbitals with 59.80 and 29.40 % weights, respectively. Similarly the transition for 21A is mainly the linear combination of HOMO-1 to LUMO and HOMO to LUMO configura tions with 28.40 and 43.60% weights in the

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115 same order. Therefore the two transitions are th e linear combinations of the orbitals with the same configurations. Basically, the coefficients which are the weights of the configurations are interchanged. This configuration behavior of th e two states indicates the mixing of these two excited states. Actually HOMO to LUMO configuration of 11A (29.40%) and HOMO to HOMO-1 configuration of 21A (28.40%) are mixing with opposite signs, -0.3843 and 0.37664 respectively, according to the comp utational data. A similar case fo r the mixing of configurations for the two excited states was reported in th e literature for a porphyrin isomer with Cs symmetry. The explanation for the mixing of the excited stat es was that it was originating from symmetry lowering of the molecular structures from D2h of porphyrin to lower Cs symmetry.148 More Cs symmetric porphyrin derivatives with split Q ba nds have been reported in the literature.131, 149 As a result in our system configuration interaction between the orbitals are enhanced and caused the splitting of the Q bands in the calculations whic h may be due to the lowering of the symmetry of the molecule. Although the subst ituents and the lowering of the symmetry affected both the electronic energy terms and the ener gies of the orbitals, splitting is not caused by the change in the orbital energies, but is cause d by the electronic energy terms.150 As mentioned before, the lowest energy transi tion in the experimental UV-Vis spectrum of transAzuleneone is at 1100 nm. The lowest transition energy is ca lculated to be at 1049.77 nm with 11Bu symmetry for 5-1b. This Q band transition is mainly from HOMO to LUMO orbital with a small contribution coming from HOMO-2 orbital. The strong contribution of HOMO-1 orbital is seen for the forbidden transition for 11Ag state at 704.71 nm with 80.40% weight for HOMO-1 to LUMO transition. There is anothe r transition calculated at 704.71 nm with 1Bu. Considering the fact that 21Bu state is almost 50% mixed with the configuration of HOMO-2, it can not be considered as pure Gouterman type transition. There are cases reported in the

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116 literature that transitions originating from low ly ing orbitals to the LUMO and LUMO+1 orbitals taking place between the Q band and the B bands.151 Basically, the low energy transitions for Q bands of the molecules are originated from HOMO-LUMO and HOMO-1-LUMO interactions for the cis isomer and HOMO-LUMO interaction for the trans isomer. The differences originating between the molecules ar e that HOMO-1-LUMO contribution for trans isomer is forbidden and it is at higher energy. The reason for this situation is that for both of the molecules the energies of the LUMO+1, LUMO and HOMO or bitals have very similar energy values. The only difference is coming from the energy of HOMO-1 orbital of trans isomer, which is more stabilized than that of cis isomer. The stabilization energy with respect to HOMO-1 orbital of cis isomer is 0.532 eV. The reason for this is that for 5-2b the electrons are delo calized all over the molecule for HOMO-1 orbital but for the cis isomer that is not the case and HOMO-1 orbital is destabilized more. 6.2.2.2 B-band regions for cis -Azuleneone and trans -Azuleneone When the rest of the spectrum for the cis isomer is considered, it is seen that there is a shoulder at 879 nm. In that region there is no single t transition calculated. This shoulder must be due to vibrational transitions. The transitions calculated at 634.12 nm, 608.38 nm, and 584.45 nm contribute to shoulders at 644 nm and 590 nm at UV-Vis spectrum. The peaks calculated at 533.86 nm and 502.69 nm are contributing to th e peak at 547 nm which has the highest absorbance in the experimental UV-Vis spectrum. The highest oscillator strength calculated for the singlet transitions is at 496.70 nm. Th e calculated peaks at 460.40 nm, 447.58 nm, and 442.37 nm correspond to the experi mental peak at 450 nm. The cal culated peaks at 414.41 nm and 400.43 nm are also in good agreem ent with the experimental data.

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117 The small peak at 762 nm observed on the experimental spectrum 5-2b might be coming from the contribution from the calculated trans ition at 710.49 nm. Experimentally the band with the highest absorbance value is at 580 nm and the peak calculated at 580 nm contributes to this band. The band with lower absorption value at 535 nm on the UV-Vis spectrum is calculated to be at 503 nm. The shoulder at 475 nm should be corresponding to the transition calculated at 457.70 nm. The transitions calculated at 440.42 nm and 431.20 nm are contributing to the peak at 427 nm on the experimental spectrum. The small peak at 850 nm is probably coming fr om vibrational transitions. The shoulder at 1220 nm (8196.72 cm) for the broad band with max at 1100 nm (9090.91 cm) must be coming from the vibrational transitions. The differen ce of energy between these two points is 894.19 cm1.The deviations between the calculated and expe rimental spectra are in acceptable range which is an indication of good agreemen t between the two spectra. When the B-band regions of both of the molecu les are considered, they both show similar trend. The region between between 400 nm a nd 600 nm has the peaks related to B-band transitions for both of the molecules. The peaks are broad and split. This is due to lowering of symmetry and the complexities of the structures. Mo lecular symmetry affects the splitting of the Soret bands.151 As presented on Table 6-3 for the B band, large number of occupied and unoccupied orbitals besides HOMO-1, HOMO, LUMO, LUMO+1 are highly contributing to the transitions. As a result it is not possible to predict the pure Soret band transitions for these molecules. Similar cases have been reported in the literature129 and explained that Gouterman model is a simple model and it does not provide explanation for the complexity of the Soret band. Therefore it is suggested that more tr ansitions, allowed and/or forbidden, should be calculated.152

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118 6.2.2.3 Oscillator strengths Comparison of the calculated and experimental oscillator strengths is more complicated due to some important error sources. Unless solva tion effect is included in the calculations, the comparison will be between the experimental data taken in solution and computed data calculated in the gas phase which is the situa tion in this work. Solvation effect may cause deviations from the expected results and su ch cases are reported in the literature.94, 153 The difficulty in the comparison of experimental and calculated data ri ses from the overlap of the electronic band with the neig hboring electronic or vibronic bands.148 Overlap of these bands creates long tails that makes the spectral band integration difficult for the prediction of experimental oscillator strengths from = 3.32 x 10-9 ( ) d where the extinction coefficient has the unit of mole-1 cm-1 and the wave number is in cm-1. This equation is approximated as it is shown below by using a single Gaussian to represent the band shape. = 3.32 x 10-9 e( / )2 d = 3.32 x 10-9 max In the equation is the half-width at = max/e which relates the full-width (h) at halfmaximum by h = 2(ln2)0.5 Band shape approximation and ba nd overlap are not the only error sources. The equations for the oscillator strength given above neglect the solvent refractive index correction. This may cause 10 to 20 percent error for common solvents.154 As a result of all these error sources it is almost impossible to determ ine the actual oscillator strength for the experimental spectrum and in this work experime ntal and theoretical oscillator strengths are not compared.

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119 6.3 Conclusion In this study, DFT level computational calculations for the molecular orbitals and the singlet excited state calculat ions were performed for the expanded porphyrin derivatives cisand transAzuleneone. The experimental and calculated structures and the spectra were compared and it was determined that they showed good agr eement. By using Goutermans theory and the calculated molecular orbitals and calculated singlet excited states of the mo lecules, the electronic spectra of the molecules were analyzed from the view of theory. Accordin g to both experimental and computational data trans isomer has more red shifted band relative to its cis analogue due to conjugation. N N O N N O Figure 6-1 Crystal structure of 5-1a.

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120 N N O N N O1 4 1 31 4 1 91 3 6 71 3 6 71 4 3 61 4 3 61 3 7 31 3 7 31 3 8 21 3 8 21 4 0 81. 40 81 3 4 31 3 4 31 3 8 01 3 8 01 4 0 61 4 0 61 4 5 01 4 5 01 3 6 71. 3 671 4 2 31 4 2 31 4 8 31 4 8 31 4 2 1 1 4 2 11 4 7 51 4 7 51 4 1 91 3 7 81 3 7 81 4 0 81.4081 4 3 81 4 3 81 4 2 91 4 291 4 3 11.4311 5 0 61 5 0 61 2 2 61 2 2 61 4 7 51 4 7 51 4 4 61 4 4 61.3 8 41 3 8 41 4 1 3 1 3 8 91 3 8 91 4 1 41 4 1 41.357 1.3571 4 2 51 4 2 5 Figure 6-2 Experimental bond lengths for 5-1a. N N O N N O1 3 9 41 4 0 71 3 7 61 3 8 21 3 871 4 1 11 3 4 61 3 9 11 4 0 81 3 9 71 4 0 41 3 4 01 4 1 61 3 8 21 3 8 91 3 8 61 4 3 41 3 8 81 4 4 01 4 7 21 2 6 11 5 0 71 4 5 21 4 2 41 4 6 01 4 3 11 4 4 61 4 7 71 3 7 41 4 6 71. 4 0 01 3 8 21.4211 4 5 71 4 2 11 3 7 61 4 0 51 3 9 71 4 5 61 3 7 61 4 6 11 4 8 31 4 4 91 3 9 21 4 2 31 4 7 11 4 3 11 3 9 81 3 8 31 4 2 01 4 2 11 4 5 81 4 2 41 4 5 11 5 0 91 2 6 21 4 6 91 3 9 71 4 0 61 3 7 6 Figure 6-3 Calculated bond lengths for 5-1b.

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121 N N N N O O1 40 81 3 9 31 3 6 01 4 0 51 3 9 41 3 7 01 3 8 31 4 0 81 3 9 41 3 9 31 3 6 01 4 0 51 3 9 41 3 7 01 3 8 31 4 4 71 3 8 21 4 6 51 2 6 21 5 1 01.4521 4 5 71 4 2 41 4 0 91. 3 951 4 0 71.3751 4 2 21 4 5 91 4 1 91 3 8 31 4 2 51.4251 4 6 91 3 8 11 4 5 51 4 4 71 3 821 4 5 71 4 6 51 2 6 21 5 1 01.4521 4 2 41 4 2 51 4 0 91 4 6 91 4 3 31 3 8 11 4 5 51 3 9 41 3 9 51 4 0 71 3 7 51 4 2 21 4 5 91 4 1 91 3 8 31 3 9 7 Figure 6-4 Calculated bond lengths for 5-2b. N4 N3 O N1 N2 O 20 1 4 5 6 9 10 11 14 15 16 19 2 3 7 8 12 13 17 18 Figure 6-5 Numbering scheme for the cis isomer for the selected atoms.

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122 Figure 6-6 Experimental and calcula ted electronic spectra for 5-1b. Figure 6-7 Experimental and calcula ted electronic spectra for 5-2b.

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123 Figure 6-8 Kohn Sham orbital energy diagrams for some of the frontier orbitals of 5-1b and 5-2b, respectively.

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124 Figure 6-9 Isoamplitude surfaces of the wave f unctions of 5-1b and 5-2b for some of their frontier orbitals, respectively.

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125 Figure 6-10 Gaussian broadening curve a nd the actual Uv-Vis spectrum for the cis isomer. Figure 6-11 Gaussian broadening curve a nd the actual Uv-Vis spectrum for the trans isomer.

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126 CHAPTER 7 SUMMARY Nuclear waste is created every day in nuc lear reactors. The wa ste contains highly radioactive actinides with very long half lives. In order to be able to convert them into shorter living nuclide transmutation is necessary. Howeve r it is not possible in the present conditions because lanthanides are present in the waste mixed with the actinides and th ey interfere with the transmutation processes by neutr on capture. This makes transmut ation of actinides impossible. As a result it is important to separate these two chemically similar metal cations from each other. For that purpose we worked with a new C3 symmetric ligand system bearing both pyridine and diamide groups together that also takes adva ntage of preorganization to provide a good coordination site for the metal. Extraction data reveal that, ligands with the lower side functionalized triphenoxymethane platform are working efficiently for the extractions of lanthanide cations when the extr action experiments were performe d in the presence of COSAN. The NMR scale extraction data clearly shows the extraction with the formation of a C3symmetric species in the solution. At a certain concentration ratio of the ligand with COSAN and the lanthanide Lu, the extraction is 100 % effi cient in the NMR timescale. Also solid state structures of the metal complexes with the uppe r side functionalized tr iphenoxymethane platform confirm the complexation of the ligand from its carbonyl and nitrogen bi nding sites. Our data with lanthanides indicate that this ligand sy stem is a promising ligand system for future application which is consistent with the recen tly reported data with the same derivative. Due to interesting spectroscopic properties of porphyrins and limited research in the expanded porphyrin systems we we re interested in the computational calculations for two expanded porhyrin derivatives cis and trans -azuleneone to be able interpret their electronic spectra. For this purpose DFT le vel computational calculations ha ve been performed successfully

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127 for these molecules with their corresponding point groups. Calculated and experimental geometries for the cis isomer are comparable. Calculated excited states are consistent with the experimental spectra. The cis isomer shows split Q band regi on because HOMO-1 to LUMO and HOMO-LUMO configurations show c onfiguration interaction. This is due to electronic affects of the substituents and symmetry lowering. For the B-band region of the spectra for both molecules, there are contributions coming from lower lying orbi tals as a result of which more transitions are observed. Both experimentally and theoretically it has been confirmed that both of the molecules are red shifted due to conjugation. HOMO-LUMO gap for trans -isomer is slightly lower so it is more red shifted than its cis analogue. This study has been one of the most detailed computational studies performe d on expanded porphyrin systems. The data was successfully interpreted with respect to molecular orbital appr oach in relevant with Goutermans theory for the porphyrin systems.

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128 APPENDIX A EXTRACTION DATA Extraction Data for 2-10: Figure A-1 Extraction plot for 1x10-3 M 2-10 in CH2Cl2 with 1x10-4 M Lanthanides in 1 M HNO3. Table A-1 Extraction data for Figure A-1. D E % E % Error La 0.145014 13 2.0 0.003647 Ce 0.170899 15 1.4 0.002635 Pr 0.17 15 1.3 0.002427 Nd 0.164319 14 3.3 0.006619 Eu 0.123725 11 1.8 0.003502 Gd 0.086409 8 0.9 0.001762 Tb 0.086556 8 0.6 0.001201 Dy 0.188371 16 2.0 0.004004 Er 0.18801 16 0.8 0.001518 Tm 0.205788 17 1.0 0.001677 Yb 0.165751 14 0.4 0.000681 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu Gd Tb Dy E r TmYb %E Lanthanides

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129 Figure A-2 Extraction plot fo r the second extraction for 1x10-3 M 2-10 in CH2Cl2 with 1x10-4 M Lanthanides in 1 M HNO3. Table A-2 Extraction fata for Figure A-2. D E % E% Error La 0.135255 12 1.1 0.001922 Ce 0.061197 6 1.2 0.002194 Pr 0.093917 9 0.9 0.001668 Nd 0.085267 8 0.4 0.00085 Eu 0.085917 8 1.0 0.002003 Gd 0.098098 9 0.9 0.001801 Tb 0.088106 8 1.1 0.002329 Dy 0.137533 12 3.7 0.007212 Er 0.10508 10 0.7 0.001405 Tm 0.133104 12 2.3 0.003971 Yb 0.128057 11 0.9 0.001477 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu Gd Tb Dy E r Tm Yb Lanthanides %E

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130 Figure A-3 Extraction plot fo r the third ex traction for 1x10-3 M 2-10 in CH2Cl2 with 1x10-4 M Lanthanides in 1 M HNO3. Table A-3 Extraction data for Figure A-3. D E % E% Error La 0.073389 7 0.5 0.000849 Ce 0.072376 7 0.1 0.000208 Pr 0.076271 7 0.5 0.000981 Nd 0.094292 9 0.6 0.001118 Eu 0.085258 8 0.4 0.000763 Gd 0.081001 7 0.1 0.000153 Tb 0.090026 8 0.5 0.001012 Dy 0.090724 8 0.8 0.001501 Er 0.10679 10 0.5 0.000949 Tm 0.091616 8 1.2 0.002021 Yb 0.11978 11 1.5 0.002287 0 10 20 30 40 50 60 70 80 90 100 LaCe P r Nd Eu Gd Tb Dy E r TmYb Lanthanides %E

PAGE 131

131 Figure A-4 Extraction plot for 7.63x10-3 M 2-10 in CH2Cl2 with 1x10-4 M Lanthanides in 1 M HNO3. Table A-4 Extraction data for Figure A-4. D E % E % Error La 0.058993 6 0.6 0.001172 Ce 0.046717 4 2.7 0.005186 Pr 0.089955 8 0.4 0.000757 Nd 0.060275 6 1.1 0.002159 Eu 0.061268 6 0.8 0.001552 Gd 0.063 6 1.3 0.002658 Tb 0.060358 6 0.7 0.001353 Dy 0.069477 6 0.8 0.001662 Er 0.118654 11 2.3 0.004366 Tm 0.041243 4 0.8 0.001473 Yb 0.079088 7 0.6 0.001044 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu Gd Tb Dy E r TmYb Lanthanides %E

PAGE 132

132 Figure A-5 Extraction plot for 1x10-3 M 2-10 in 1-Octanol with 1x10-4 M Lanthanides in 1 M HNO3. Table A-5 Extraction data for Figure A-5. D E % E % Error La -0.03556 -4 0.9 0.00165 Ce -0.03205 -3 0.7 0.001212 Pr -0.00196 0 3.8 0.007151 Nd -0.03465 -4 0.2 0.000473 Eu -0.05016 -5 0.5 0.00105 Gd -0.03544 -4 1.0 0.002021 Tb -0.02526 -3 0.1 0.000252 Dy -0.02143 -2 0.4 0.000757 Er 0.003156 0 0.8 0.001473 Tm 0.01445 1 1.0 0.001735 Yb 0.023555 2 1.4 0.00215 -10 0 10 20 30 40 50 60 70 80 90 100 LaCe P r NdEuGdTbDyE r TmYb Lanthanides %E

PAGE 133

133 Figure A-6 Extraction plot for 1x10-2 M 2-10 in 1, 2-dichloroethane with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3. Table A-6 Extraction data for Figure A-6. D E % E% Error La N/A N/A N/A N/A Ce 0.004431 0 0.1 0.000231 Pr N/A N/A N/A N/A Nd 0.004873 0 0.1 0.000153 Eu 0.00483 0 0.6 0.001069 Gd N/A N/A N/A N/A Tb 0.01404 1 0.2 0.0004 Dy N/A N/A N/A N/A Er N/A N/A N/A N/A Tm 0.079635 7 0.1 0.000153 Yb 0.086155 8 0.6 0.000987 -10 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu Gd TbDy Er Tm Yb Lanthanides %E

PAGE 134

134 Extraction Data for 2-11: Figure A-7 Extraction plot for 1x10-3 M 2-11 in CH2Cl2 with 1x10-4 M Lanthanides in 1 M HNO3. Table A-7 Extraction Data for Figure A-7. D E % E% Error La 0.075269 7 1.3 0.002364 Ce 0.038589 4 1.9 0.003581 Pr 0.083124 8 4.4 0.008262 Nd 0.06983 7 3.2 0.006281 Eu 0.062891 6 0.4 0.000839 Gd 0.051791 5 2.6 0.005216 Tb 0.009059 1 1.7 0.003453 Dy 0.072717 7 2.3 0.004521 Er 0.043338 4 0.8 0.001582 Tm 0.033668 3 0.5 0.0009 Yb 0.051034 5 1.1 0.001735 -10 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu Gd Tb Dy E r TmYb Lanthanides %E

PAGE 135

135 Extraction Data for 2-12: Figure A-8 Extraction plot for 1x10-3 M 2-12 in CH2Cl2 with 1x10-4 M Lanthanides in 1 M HNO3. Table A-8 Extraction data for Figure A-8. D E % E % Error La 0.031274 3 0.9 0.001601 Ce 0.043884 4 2.3 0.004444 Pr 0.051061 5 0.9 0.001716 Nd 0.037865 4 0.3 0.000643 Eu 0.080184 7 1.1 0.002329 Gd 0.028457 3 0.5 0.001172 Tb 0.055407 5 0.2 0.000404 Dy 0.046512 4 0.8 0.001652 Er 0.022731 2 0.1 0.0003 Tm 0.020428 2 0.4 0.0007 Yb 0.046141 4 0.4 0.000577 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu Gd TbDy Er Tm Yb Lanthanides %E

PAGE 136

136 Figure A-9 Extraction plot fo r the second extraction for 1x10-3 M 2-12 in CH2Cl2 with 1x10-4 M Lanthanides in 1 M HNO3. Table A-9 Extraction data for Figure A-9. D E % E % Error La 0.009649 1 1.1 0.002043 Ce 0.007234 1 0.7 0.001405 Pr 0.039457 4 1.1 0.002157 Nd 0.010294 1 1.2 0.002411 Eu 0.043686 4 0.4 0.000814 Gd 0.039487 4 0.6 0.00132 Tb 0.026457 3 0.5 0.001115 Dy 0.01436 1 1.8 0.003544 Er -0.01002 -1 0.3 0.000557 Tm -0.00131 0 1.8 0.003291 Yb 0.003877 0 2.7 0.004405 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu Gd TbDy Er Tm Yb Lanthanides %E

PAGE 137

137 Extraction Data for 2-13: Figure A-10 Extraction plot for 1x10-3 M 2-13 in CH2Cl2 with 1x10-4 M Lanthanides in 1 M HNO3. Table A-10 Extraction data for Figure A-10. D E % E % Error La 0.12111 11 3.6 0.006345 Ce 0.059809 6 1.8 0.003291 Pr 0.07676 7 1.1 0.00206 Nd 0.070052 7 1.7 0.003232 Eu 0.052965 5 0.6 0.001136 Gd 0.0729 7 1.5 0.003024 Tb 0.068024 6 0.6 0.001127 Dy 0.108818 10 3.0 0.005987 Er 0.114496 10 0.7 0.001277 Tm 0.129527 11 1.3 0.002248 Yb 0.103874 9 3.0 0.004676 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu Gd Tb Dy E r TmYb Lanthanides %E

PAGE 138

138 Figure A-11 Extraction plot fo r the second extraction for 1x10-3 M 2-13 in CH2Cl2 with 1x10-4 M Lanthanides in 1 M HNO3. Table A-11 Extraction data for Figure A-11. D E % E % Error La 0.083299 8 1.9 0.003444 Ce 0.075311 7 1.1 0.001955 Pr 0.063429 6 0.9 0.001609 Nd 0.085338 8 0.5 0.001012 Eu 0.071954 7 1.0 0.001922 Gd 0.087781 8 1.3 0.002702 Tb 0.058083 5 0.8 0.001637 Dy 0.076503 7 0.9 0.001838 Er 0.092951 9 1.3 0.0024 Tm 0.10835 10 1.7 0.002821 Yb 0.12503 11 1.8 0.002715 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu Gd Tb Dy E r TmYb Lanthanides %E

PAGE 139

139 Figure A-12 Extraction plot fo r the third extraction for 1x10-3 M 2-13 in CH2Cl2 with 1x10-4 M Lanthanides in 1 M HNO3. Table A-12 Extraction data for Figure A-12. D E % E% Error La 0.119228 11 4.2 0.007495 Ce 0.167633 14 2.3 0.004243 Pr 0.121535 11 0.7 0.00121 Nd 0.117693 11 2.3 0.004349 Eu 0.117399 11 0.5 0.000945 Gd 0.164662 14 2.1 0.004382 Tb 0.096446 9 0.7 0.00135 Dy 0.125714 11 1.0 0.002022 Er 0.145987 13 2.8 0.005233 Tm 0.180952 15 0.2 0.000361 Yb 0.165915 14 0.4 0.000693 0 10 20 30 40 50 60 70 80 90 100 LaCe P r Nd Eu GdTb Dy E r TmYb Lanthanides %E

PAGE 140

140 Figure A-13 Extraction plot for 1x10-4 M 2-13 in 1, 2-dichloroethane with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3. Table A-13 Extraction data for Figure A-13. D E % E % Error La 5.792357 85 0.3 0.000513 Ce 5.983312 86 0.3 0.000462 Pr 7.9328 89 1.3 0.00245 Nd 5.784959 85 1.6 0.003083 Eu 3.957447 80 3.5 0.006735 Gd 3.470418 78 3.5 0.007146 Tb 3.608859 78 5.2 0.010615 Dy 2.476471 71 0.4 0.000764 Er 2.47424 71 2.4 0.004518 Tm 1.691371 63 4.6 0.007749 Yb 2.13266 68 1.1 0.001769 0 10 20 30 40 50 60 70 80 90 100 LaCe P r Nd Eu Gd TbDy E r Tm Yb Lanthanides %E

PAGE 141

141 Figure A-14 Extraction plot fo r the second extraction for 1x10-4 M 2-13 in 1, 2-dichloroethane with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3. Table A-14 Extraction data for Figure A-14. D E % E % Error La 7.042324 88 0.9 0.001704 Ce 12.07993 92 0.5 0.000872 Pr 7.336691 88 1.0 0.001893 Nd 6.597772 87 0.5 0.001041 Eu 8.7344 90 1.8 0.00363 Gd 3.166586 76 0.5 0.001044 Tb 5.003693 83 0.6 0.001353 Dy 4.824602 83 6.2 0.012831 Er 6.123995 86 0.5 0.001041 Tm 6.590986 87 14.3 0.026872 Yb 4.77633 83 1.6 0.002857 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu Gd TbDy Er Tm Yb Lanthanides %E

PAGE 142

142 Figure A-15 Extraction plot fo r the third extraction for 1x10-4 M 2-13 in 1, 2-dichloroethane with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3. Table A-15 Extraction data for Figure A-15. D E % E % Error La 7.255523 88 1.3 0.002386 Ce 6.896304 87 1.7 0.003242 Pr 7.348703 88 0.7 0.001343 Nd 6.645081 87 1.3 0.002706 Eu 3.820919 79 3.7 0.007411 Gd 4.424473 82 1.5 0.003297 Tb 4.243548 81 4.5 0.009782 Dy 3.227088 76 4.1 0.008433 Er 2.173913 68 2.3 0.004654 Tm 4.02852 80 6.2 0.011692 Yb 3.639581 78 2.7 0.004693 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu Gd TbDy Er Tm Yb %E Lanthanides

PAGE 143

143 Figure A-16 Extraction plot for 1x10-3 M 2-13 in 1, 2-dichloroethane with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3. Table A-16 Extraction data for Figure A-16. D E % E % Error La 2.578523 72 0.2 0.000321 Ce 12.23601 92 0.5 0.000985 Pr 24.72811 96 0.1 0.000252 Nd 25.60829 96 0.6 0.001159 Eu 19.01718 95 0.2 0.000458 Gd 8.561728 90 0.7 0.00148 Tb 16.29296 94 0.3 0.000603 Dy 66.93103 99 1.1 0.002138 Er 6.838936 87 2.1 0.003923 Tm 4.738149 83 0.9 0.001557 Yb 4.371824 81 2.2 0.00335 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu Gd TbDy Er Tm Yb Lanthanides %E

PAGE 144

144 Figure A-17 Extraction plot fo r the second extraction for 1x10-3 M 2-13 in 1, 2-dichloroethane with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3. Table A-17 Extraction data for Figure A-17. D E % E % Error La 1.675842 63 1.7 0.003166 Ce 6.427606 87 0.6 0.001136 Pr 8.72621 90 1.9 0.003696 Nd 3.753679 79 4.8 0.009828 Eu 7.958333 89 1.3 0.002696 Gd 15.05941 94 0.3 0.000551 Tb 4.580183 82 9.4 0.02011 Dy 14.25616 93 2.0 0.00412 Er 2.383899 70 4.4 0.009037 Tm 1.953846 66 13.8 0.02556 Yb 3.521108 78 18.7 0.031988 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu Gd TbDy Er Tm Yb Lanthanides %E

PAGE 145

145 Extraction Data for 2-14: Figure A-18 Extraction plot for 1x10-3 M 2-14 in 1, 2-dichloroethane with 3x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3. Table A-18 Extraction data for Figure A-18. D E % E % Error La 5534.75 100 0.7 0.001258 Ce 22.48742 96 3.6 0.00678 Pr 6.294494 86 0.7 0.00132 Nd 14.94819 94 4.0 0.008278 Eu 10.5239 91 7.9 0.015915 Gd 2.744684 73 2.5 0.005359 Tb 5.148112 84 1.4 0.002937 Dy 2.445022 71 2.5 0.005125 Er 3.688668 79 7.8 0.015698 Tm 1.995948 67 0.1 0.0001 Yb 1.286418 56 3.8 0.006294 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu Gd TbDy Er Tm Yb Lanthanides %E

PAGE 146

146 Extraction Data for 2-15: Figure A-19 Extraction plot for 1x10-3 M 2-15 in 1-Octanol with 1x10-4 M Lanthanides in 1 M HNO3. Table A-19 Extraction data for Figure A-19. D E % E % Error La -0.06512 -7 2.3 0.004244 Ce -0.01518 -2 0.5 0.000981 Pr -0.01526 -2 0.3 0.000557 Nd -0.03367 -3 0.2 0.000458 Eu -0.023 -2 0.1 0.000252 Gd -0.02529 -3 0.9 0.001973 Tb -0.02991 -3 0.1 0.000173 Dy -0.01953 -2 0.8 0.001677 Er -0.01744 -2 0.3 0.000666 Tm -0.02124 -2 0.4 0.000666 Yb -0.02323 -2 0.1 0.0002 -20 -10 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu Gd TbDy Er Tm Yb Lanthanides %E

PAGE 147

147 Figure A-20 Extraction plot fo r the second extraction for 1x10-3 M 2-15 in 1-Octanol with 1x10-4 M Lanthanides in 1 M HNO3. Table A-20 Extraction data for Figure A-20. D E % E % Error La -0.03686 -4 0.3 0.000529 Ce -0.05748 -6 1.4 0.002598 Pr -0.04829 -5 1.2 0.002272 Nd -0.0535 -6 1.2 0.002476 Eu -0.0601 -6 0.4 0.000737 Gd -0.05457 -6 0.6 0.001222 Tb -0.0658 -7 0.3 0.0006 Dy -0.0543 -6 0.9 0.001888 Er -0.02391 -2 0.6 0.001229 Tm -0.01312 -1 0.6 0.001124 Yb -0.02137 -2 0.9 0.00155 -20 -10 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu GdTb Dy E r TmYb Lanthanides E%

PAGE 148

148 Figure A-21 Extraction plot fo r the third extraction for 1x10-3 M 2-15 in 1-Octanol with 1x10-4 M Lanthanides in 1 M HNO3. Table A-21 Extraction data for Figure A-21. D E % E % Error La -0.04782 -5 1.0 0.001848 Ce -0.04641 -5 0.8 0.001626 Pr -0.03401 -4 0.2 0.000473 Nd -0.0259 -3 0.2 0.000403 Eu -0.02394 -2 0.3 0.000613 Gd -0.03599 -4 0.2 0.000473 Tb -0.02825 -3 0.9 0.001966 Dy -0.02574 -3 0.4 0.000777 Er -0.02414 -2 0.3 0.000661 Tm -0.02892 -3 1.3 0.002369 Yb -0.04223 -4 0.1 0.000115 -20 -10 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu Gd TbDy Er Tm Yb Lanthanides %E

PAGE 149

149 Figure A-22 Extraction plot for 1x10-3 M 2-15 in 1-Octanol with 3x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3. Table A-22 Extraction data for Figure A-22. D E % E % Error La -0.03835 -4 0.1 0.0002 Ce -0.01297 -1 0.2 0.000361 Pr -0.00571 -1 0.3 0.000666 Nd -0.02437 -2 1.1 0.002291 Eu 0.000818 0 0.4 0.000794 Gd -0.00078 0 0.2 0.0005 Tb -0.00613 -1 0.6 0.0012 Dy 0.01419 1 1.0 0.001973 Er 0.004164 0 0.2 0.000493 Tm -0.00373 0 0.5 0.000896 Yb -0.00826 -1 0.7 0.001222 -10 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu Gd TbDy Er Tm Yb Lanthanides %E

PAGE 150

150 Figure A-23 Extraction plot for 1x10-3 M 2-15 in CH2Cl2 with 3x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3. Table A-23 Extraction data for Figure A-23. D E % E % Error La 99.75926 99 0.2 0.000436 Ce 119.8254 99 0.1 0.000263 Pr 87.35385 99 0.2 0.000416 Nd 108.6396 99 0.2 0.000404 Eu 96.07937 99 0.6 0.001211 Gd 106.9662 99 0.2 0.000519 Tb 98.2 99 0.4 0.000907 Dy 134.0 99 0.2 0.000346 Er 63.30933 98 0.3 0.00066 Tm 90.36752 99 0.4 0.000785 Yb 91.83019 99 0.4 0.000643 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu Gd TbDy Er Tm Yb %E Lanthanides

PAGE 151

151 Figure A-24 Extraction plot fo r the second extraction for 1x10-3 M 2-15 in CH2Cl2 with 3x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3. Table A-24 Extraction data for Figure A-24. D E % E % Error La 2719.5 100 0.3 0.000473 Ce 258.5 100 0.7 0.001286 Pr 3827.667 100 0.3 0.000495 Nd 4055.667 100 0.0 7.07E-05 Eu 138.0 99 0.5 0.001106 Gd 356.389 100 0.1 0.000183 Tb 123.0 99 0.3 0.000693 Dy 606.5 100 0.1 0.000252 Er 46.10156 98 0.4 0.000902 Tm 2671.5 100 0.0 5.77E-05 Yb 377.4615 100 0.2 0.000289 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu Gd TbDy Er Tm Yb %E Lanthanides

PAGE 152

152 Figure A-25 Extraction plot fo r the third extraction for 1x10-3 M 2-15 in CH2Cl2 with 3x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3. Table A-25 Extraction data for Figure A-25. D E % E % Error La -132.123 101 0.2 0.000419 Ce -112.464 101 0.3 0.000568 Pr -3863.67 100 0.1 0.000265 Nd -104.612 101 0.1 0.000275 Eu -123.909 101 0.1 0.000252 Gd -98.3939 101 0.1 0.000231 Tb -99.5152 101 0.1 0.000183 Dy 1036.75 100 0.8 0.001738 Er -91.9158 101 0.2 0.000492 Tm -126.378 101 0.7 0.001288 Yb -70.47 101 0.2 0.000346 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu Gd TbDy Er Tm Yb Lanthanides %E

PAGE 153

153 Figure A-26 Extraction plot for 1x10-4 M 2-15 in 1, 2-dichloroethane with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3. Table A-26 Extraction data for Figure A-26. D E % E % Error La 0.19983 17 0.9 0.001686 Ce 0.284212 22 0.3 0.0006 Pr 0.286093 22 1.2 0.002261 Nd 0.281746 22 0.6 0.001229 Eu 0.372033 27 1.2 0.002468 Gd 0.23581 19 1.1 0.002402 Tb 0.334997 25 2.0 0.004251 Dy 0.258432 21 0.6 0.001159 Er 0.204249 17 0.8 0.001721 Tm 0.191526 16 1.6 0.003027 Yb 0.156468 14 3.2 0.005559 -3 7 17 27 37 47 57 67 77 87 97 La Ce P r Nd Eu Gd TbDy Er Tm Yb Lanthanides %E

PAGE 154

154 Extraction Data for 2-16: Figure A-27 Extraction plot for 1x10-3 M 2-16 in CH2Cl2 with 1x10-4 M Lanthanides in 1 M HNO3. Table A-27 Extraction data for Figure A-27. D E % E % Error La 0.031845 3 0.3 0.000513 Ce 0.03446 3 0.3 0.000513 Pr 0.030968 3 0.9 0.001739 Nd 0.027285 3 0.6 0.001168 Eu 0.025866 3 0.7 0.001442 Gd 0.03725 4 0.3 0.000557 Tb 0.019533 2 0.1 0.0002 Dy 0.006009 1 0.2 0.000321 Er 0.021154 2 0.1 0.0003 Tm 0.031302 3 1.3 0.002386 Yb 0.015307 2 0.2 0.000416 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu Gd TbDy Er Tm Yb Lanthanides %E

PAGE 155

155 Figure A-28 Extraction plot fo r 1x10-4 M 2-16 in 1, 2-dichlo roethane with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3. Table A-28 Extraction data for Figure A-28. D E % E% Error La 0.055015 5 0.3 0.000513 Ce 0.072324 7 0.2 0.000361 Pr 0.049352 5 0.6 0.001097 Nd 0.066007 6 0.3 0.000529 Eu 0.059754 6 2.3 0.004631 Gd 0.038412 4 1.3 0.002859 Tb 0.032985 3 0.7 0.001401 Dy 0.023125 2 0.5 0.001015 Er 0.042078 4 0.9 0.001907 Tm 0.000899 0 1.2 0.002194 Yb 0.021613 2 0.7 0.001212 -10 0 10 20 30 40 50 60 70 80 90 100 La Ce P r Nd Eu Gd TbDy Er Tm Yb Lanthanides %E

PAGE 156

156 Figure A-29 Extraction plot fo r the second extraction for 1x10-4 M 2-16 in 1, 2-dichloroethane with 1x10-3 M COSAN with 1x10-4 M Lanthanides in 1 M HNO3. Table A-29 Extraction data for Figure A-29. D E % E % Error La 0.006067 1 0.8 0.001411 Ce 0.060697 6 0.6 0.001201 Pr 0.042032 4 0.8 0.001604 Nd 0.03613 3 0.5 0.000971 Eu 0.029659 3 0.3 0.000513 Gd 0.028494 3 0.7 0.001434 Tb 0.016024 2 1.1 0.002428 Dy -0.00797 -1 0.4 0.000896 Er -0.01718 -2 0.4 0.000833 Tm -0.00108 0 0.2 0.0004 Yb -0.0158 -2 0.5 0.000913 -3 7 17 27 37 47 57 67 77 87 97 La Ce P r Nd Eu Gd TbDy Er Tm Yb %E Lanthanides

PAGE 157

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166 BIOGRAPHICAL SKETCH Ozge Ozbek was born on November 26, 1976, in Izmir, Turkey. She started her undergraduate studies in Chemistry in 1996 in A dvanced Program (Honor Group) at Middle East Technical University, in Ankara Turkey. She continued her underg raduate studies in Advanced Program until she received her B achelors Degree in chemistry. During her undergraduate years, she did undergraduate research studies on the sy nthesis and electronic sp ectroscopy of binuclear rhodium complexes under the supervision of Dr. Hseyin I i. She received her Bachelors Degree in chemistry in June, 2000. Three months af ter her graduation, she started her studies for Master of Science in chemistry. At the same time she became teaching assistant at the Chemistry Department at Middle East Technical Univers ity. During her graduate years, she worked on electrochemical and spectroscopic properties of binuclear platinum complexes under the supervision of Dr. Hseyin I i and co-supervision of Dr. Ahme t M. nal. In July 2002, she received her Masters Degree in chemistry. Sh e came to University of Florida in August 2002 and started her studies for Doctor in Philosophy Degree (Ph.D.) in the Chemistry Department in Inorganic Division under the superv ision of Dr. Michael J. Scott. During her Ph.D. studies, she worked on both computational and experiment al projects. She performed computational calculations on expanded porphyrin systems and worked on the synthesis of ligands for the nuclear waste reprocessing studies. She r eceived her Ph.D. in December, 2007.