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Synthesis and Characterization of Lanthanide Complexes for Use in Near-Infrared Light Emitting Diodes

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PAGE 1

SYNTHESIS AND CHARACTERIZATION OF LANTHANIDE COMPLEXES FOR USE IN NEAR-INFRARED LIGHT EMITTING DIODES By ALISON STEELE KNEFELY 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 2005

PAGE 2

This document is dedicated to my grandpa rents RADM and Mrs. Richard A. Paddock and Mr. and Mrs. George M. Knefely, Sr., my parents Dr. and Mrs. George M. Knefely, Jr. and my loving husband Charles Robert Sides.

PAGE 3

ACKNOWLEDGMENTS First of all, I would like to thank my advisor, Jim Boncella, for all of his guidance, understanding and support throughout my graduate career. I would like to also thank him for the opportunity to work at Los Alamos National Lab, where I had the privilege to meet and work with other great scientists. I would like to thank Tony Burrell for taking me under his wing at LANL and for sharing his knowledge of porphyrin chemistry and electrochemistry. I would like to thank all the people who made it a smooth transfer to and from the lab, especially Bill Tumas, Bev Ortiz and Deb Allison-Truijillo. I would like to thank my dear friends and colleagues, especially Edel Minogue, Paul and Isabel Plieger, Gavin Collis, Piyush Shulka and the Burrell and Boncella families who not only helped in chemistry, but made me a part a family, provided tennis partners and made living in Los Alamos enjoyable and memorable. I would like to thank Kirk Schanze and all the members of the group who provided a bench, hood, desk and a group of great people with whom to work. I would like to thank Lisa McElwee-White and all of the group members who provided a glove box and solvent system for me to use. I would like to thank the former members of the Boncella group, especially Elon Ison, Tim Foley and Tom Cameron, for all of their friendship and guidance. I would like to thank all the collaborators who have come together to make this work possible, especially Khalil Abboud, Brian Scott, John Reynolds, Paul Holloway, Ben Harrison, Garry Cunningham, T.S. King Nisha Ananthakrishnan and Fengui Guo. I would like to thank my undergraduate research advisor, R. Chris iii

PAGE 4

Schnabel. Without his love for chemistry, I would not have developed a taste for synthetic chemistry and without his guidance, I would not have pursued a career in chemistry. I would like to thank my parents whose love and support have carried me through all of these years. I thank my entire family, the Knefelys, Paddocks, Stumpfs and Sides, for all of their encouragement. Finally, I would like to thank my husband Rob for giving me the love, strength and laughter to finish and make it a fun ride. iv

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TABLE OF CONTENTS page ACKNOWLEDGMENTS.................................................................................................iii TABLE.............................................................................................................................viii LIST OF FIGURES...........................................................................................................ix ABSTRACT.....................................................................................................................xiii CHAPTER 1 INTRODUCTION........................................................................................................1 2 LANTHANIDE TETRAPHENYLPORPHYRIN COMPLEXES: SYNTHESIS, CHARACTERIZATION AND LUMINESCENCE STUDIES.................................11 Introduction.................................................................................................................11 Previous Synthetic Procedures...................................................................................12 Synthesis of Nd and Pr Complexes............................................................................14 Half-Sandwich Complexes..................................................................................14 LnTPPI(DME) Complexes..................................................................................16 LnTPP(L) Complexes..........................................................................................18 LnTPP(Tp) complexes.................................................................................19 LnTPP(LOEt) complexes.............................................................................21 LnTPP(quinolate) complexes.......................................................................23 NMR Studies..............................................................................................................24 NdTPPTp.............................................................................................................25 NdTPP(LOEt)......................................................................................................29 LnTPP(L) Photoluminescence and Electroluminescene Studies................................32 Summary and Conclusions.........................................................................................35 Experimental...............................................................................................................36 Materials and Reagents........................................................................................36 Synthesis..............................................................................................................37 NdI 3 (THF) 4 (1).............................................................................................37 PrI 3 (THF) 4 (2)...............................................................................................38 NdTPPI(DME) (3)........................................................................................38 PrTPPI(DME) (4).........................................................................................39 GdTPP(Cl)DME (5).....................................................................................39 LuTPP(Cl)DME (6)......................................................................................39 v

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NdTPPTp (7)................................................................................................40 PrTPPTp (8).................................................................................................40 GdTPPTp (9)................................................................................................41 LuTPPTp (10)..............................................................................................41 NdTPP(LOEt) (11).......................................................................................42 PrTPP(LOEt) (12)........................................................................................42 YbTppQ(THF) (13)......................................................................................43 X-ray....................................................................................................................43 NdTPPI(THF) 2 .............................................................................................43 LuTPPCl(DME)...........................................................................................44 NdTPPTP.....................................................................................................45 YbTppQ(THF).............................................................................................46 3 LANTHANIDE SUBSTITUTED TETRA(ARYL)PORPHYRIN AND PHTHALOCYANINE COMPLEXES : SYNTHESIS, CHARACTERIZATION AND LUMINESCENCE STUDIES..........................................................................47 Substituted Tetra(aryl)porphyrins...............................................................................47 Synthesis..............................................................................................................48 NMR Studies.......................................................................................................50 Electrochemistry..................................................................................................52 Photoluminescence and Electroluminescene Studies..........................................61 Summary..............................................................................................................63 Lanthanide-Phthalocyanine Complexes.....................................................................63 Synthesis and Structure of LnPc(LOEt) Complexes...........................................64 NMR Studies.......................................................................................................67 Photoluminescence Studies.................................................................................68 Summary..............................................................................................................69 Experimental...............................................................................................................69 Materials and Reagants........................................................................................69 Synthesis..............................................................................................................70 Yb(TMPP)Cl(DME) (14).............................................................................70 Yb(TMPP)Tp (15)........................................................................................71 4(2-ethylhexyloxy)benzaldehyde (16) 96 .......................................................71 5,10,15,20-tetrakis [4-(2-ethylhexyloxy) phenyl]-porphyrin (TPPoeh) (17)..........................................................................................................72 Li 2 TPPoeh(DME) 4 (18)................................................................................72 YbTPPoehCl(DME) (19).............................................................................73 YbTPPoeh(Tp) (20)......................................................................................73 Li 2 TPyP(DMF) 2 (21)....................................................................................74 YbTPyPCl(DME) (22).................................................................................74 YbTPyP(LOEt) (23).....................................................................................75 NdPcI(DME) (24)........................................................................................75 PrPcI(DME) (25)..........................................................................................76 NdPc(LOEt) (26)..........................................................................................76 PrPc(LOEt) (27)...........................................................................................76 HoPc(LOEt) (28)..........................................................................................77 vi

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TmPc(LOEt) (29).........................................................................................77 XRAY of PrPc(LOEt).........................................................................................78 4 POLYERMIZABLE LANTHANIDE-PORPHYRIN COMPLEXES.......................79 Introduction.................................................................................................................79 Lanthanide Polymers...........................................................................................79 Porphyrin Polymers.............................................................................................80 Lanthanide-Porphyrin Polymer Complexes...............................................................82 Lanthanide-vinylporphyrin Complexes...............................................................82 Synthesis.......................................................................................................82 NMR studies.................................................................................................86 Metathesis reactions.....................................................................................88 Polymerization.............................................................................................93 Tp Polymer..........................................................................................................95 Summary.....................................................................................................................97 Experimental...............................................................................................................99 Materials and Reagents........................................................................................99 Synthesis............................................................................................................100 TPPv (30)...................................................................................................100 Li 2 TPPv(DME) 2 (31)..................................................................................101 YbTPPvCl(DME) (32)...............................................................................101 YbTPPv(Tp) (33).......................................................................................102 YbTPPv(LOEt) (34)...................................................................................102 TPP-TPP (35).............................................................................................103 YbTPPTp-YbTPPTp (36)..........................................................................103 YbTPP-Tp polymer (37)............................................................................104 Copolymerizations.....................................................................................104 5 CONCLUSIONS......................................................................................................106 Crystallographic information...........................................................................................110 LIST OF REFERENCES.................................................................................................124 BIOGRAPHICAL SKETCH...........................................................................................131 vii

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TABLE Table page Table 3.1: Half wave potentials and band gaps of Ln-porphyrin complexes (potentials are reported vs Fc/Fc + internal standard).................................................................61 viii

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LIST OF FIGURES Figure page 1.1: Examples of compounds used as emitters in OLEDs. 2 .............................................1 1.2: Configuration of multi-layer device and molecular structures..................................2 1.3: Configuration of a typical multi-layer device...........................................................4 1.4: Common organic molecules for hole and electron transport....................................5 1.5: Commonly used conjugated polymers for emission in device construction.............5 1.6: Scheme of Dexter and Forster energy transfer mechanisms.....................................6 1.7: Ir(acac) dopants for OLEDs......................................................................................7 1.8: Energy transfer from chromophore to lanthanide metal center for sensitized emission......................................................................................................................8 1.9: Normalized luminescence of Yb 3+ Nd 3+ Er 3+ Ho 3+ and Tm 3+ 24 .............................9 2.1: Synthesis of LnTPPCl(DME) where Ln = Ho, Er, Tm, and Yb.............................13 2.2: Synthesis of LnTPP(L) complexes (Ln= Ho, Er, Tm,Yb and L= Tp,L(OEt))........14 2.3: Synthesis of NdTpCl 2 (THF) 2 ..................................................................................15 2.4: Synthesis of 3 and 4................................................................................................16 2.5: Thermal ellipsoid plots of the molecular structure of NdTPPI(DME) (top) and LuTPPCl(DME) (6) (bottom), showing selected atom labels, drawn at the 50 % probability level. The hydrogen atoms have been excluded for clarity...................18 2.6: Synthesis of LnTPP(Tp) where Ln = Pr, Nd, Gd, Lu..............................................20 2.7: Thermal ellipsoid plot of NdTPPTp (7) showing selected atom labels drawn at the 50 % probability level. The hydrogen atoms have been excluded for clarity....21 2.8: Synthesis of LnTPP(LOEt), where Ln = Nd (11), Pr (12)......................................22 2.9: Synthesis of YbTPP(Q)THF (13)............................................................................23 ix

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2.10: Thermal ellipsoid plot of YbTPP(Q)THF (13) showing selected atom labels drawn at the 50 % probability level. The hydrogen atoms have been excluded for clarity..................................................................................................................24 2.11: 1 H NMR of NdTPPTp (7).......................................................................................26 2.12: Variable temperature NMR of the phenyl region of NdTPPTp (7) from 20-50..27 2.13: Full COSY NMR of NdTPPTp (7) (top), expansion from 8.5-5.5 ppm (bottom)..28 2.14: 1 H NMR spectrum of NdTPP(LOEt) (11)...............................................................30 2.15: COSY NMR of NdTPP(LOEt) (11)........................................................................31 2.16: COSY NMR of NdTPP(LOEt) (11), expansion from 8-2ppm...............................31 2.17: PL emission NdTPPL (solid lines, L = Tp, dashed lines, L = LOEt).....................32 2.18: Device architecture..................................................................................................33 2.19: Charge hopping cartoon..........................................................................................34 2.20: Electroluminescence emission of Ln(TPP)(LOEt) in polystyrene measured at 9 V. Ln = Nd (solid line), Yb (dashed line) and Er (dotted line). 74 ............................34 3.1: Synthesis of YbTmPP(Cl)DME (14), YbTPPoeh(Cl)DME (19), and YbTPyP(Cl)DME (22).............................................................................................48 3.2: Synthesis of Yb(TmPP)Tp (15), Yb(TPPoeh)Tp (20) and Yb(TPyP)L(OEt) 3 (23)...........................................................................................................................50 3.3: Proton NMR spectrum of Yb(TmPP)Cl(DME) (14) in DMSO-d 6 (*)....................51 3.4: Proton NMR of Yb(TPyP)L(OEt) 3 (23) in C 6 D 6 ( denotes silicon grease impurity)...................................................................................................................52 3.5: 1-Butyl-1-methyl-pyrrolidium bis(trifluoromethyl)sulfonamide ([BMP + ]-[NTF ]), ionic liquid used for electrochemical studies......................................................53 3.6: Cyclic voltamogram of [BMP + ]-[NTF ]..................................................................53 3.7: CV of a reversible reduction and reoxidation.........................................................54 3.8: Electrode reaction mechanism of LnTPP(acac)......................................................55 3.9: CV of TmPP in ionic liquid with a scan rate of 0.1 V/s ( indicates Fc/Fc + )..........55 3.10: Cyclic voltammogram of 15 in ionic liquid with a scan rate of 0.3 V/s ( indicates Fc/Fc + ).......................................................................................................56 x

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3.11: Cyclic voltammogram of TPyP in ionic liquid with a scan rate of 0.3 V/s............57 3.12: Cyclic voltammogram of the oxidation (left) and reduction (right) ofYbTPyP(LOEt) in ionic liquid with a scan rate of 0.3 V/s...................................58 3.13: Cyclic voltammogram of YbTPPTp in ionic liquid with a scan rate of 0.2 V/s ( indicates Fc/Fc + ).......................................................................................................58 3.14: Cyclic voltammogram ofYbTPP(LOEt) in ionic liquid with a scan rate of 0.05 V/s ( indicates Fc/Fc + ).............................................................................................59 3.15: Electroluminescence of Yb(TMPP)TP (bottom), Yb(TPyP)L(OEt) 3 (middle), and Yb(TPPoeh)TP (top) as a function of increasing voltage, starting at 6 V to 20 V..........................................................................................................................62 3.16: Phthalocyanine (Pc).................................................................................................64 3.17: Synthesis of LnPcI(DME), Ln= Nd, Pr...................................................................65 3.18: Synthesis of LnPc(LOEt) complexes, Ln = Pr, Nd.................................................65 3.19: Solid state structure of PrPc(LOEt) (27).................................................................66 3.20: 1 H NMR spectrum of PrPc(LOEt) (27)...................................................................67 3.21: COSY NMR spectra of PrPc(LOEt) (27)................................................................68 3.22: Expansion of COSY NMR spectra of PrPc(LOEt) (27).........................................68 4.1: Eu(TTA) 2 (VBA)phen-NVK copolymer..................................................................80 4.2: Structure of porphyrin supported in polyaniline.....................................................81 4.3: Examples of porphyrin polymers............................................................................82 4.4: Synthesis of TPPv...................................................................................................83 4.5: Synthesis of vinylporphyrin by Pomogailo et al.....................................................84 4.6: Synthesis of 32........................................................................................................85 4.7: Synthesis of complexes 33 and 34..........................................................................85 4.8: 1 H NMR spectrum of YbTPPvTp (33)....................................................................86 4.9: COSY NMR of 33 (top), expansion from 11-6 ppm (bottom)................................87 4.10: Catalytic cycle for metathesis reaction between vinyl porphyrins..........................88 xi

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4.11: P1PH NMR spectrum of 35 (aromatic region of 30 in inset)......................................90 4.12: Synthesis of 36........................................................................................................91 4.13: 1 H NMR spectrum of the phenyl region of 36 (33 in inset)....................................92 4.14: 2-D NMR spectrum of the phenyl region of 36......................................................92 4.15: Scheme of a free radical chain growth mechanism.................................................93 4.16: Chemical structures of monomers...........................................................................94 4.17: Structure of Tp polymer..........................................................................................95 4.18: Synthesis of YbTPP-Tp (37) polymer.....................................................................96 4.19: Absorption spectrum of 37 (inset shows Q bands).................................................97 4.20: NIR emission spectrum of 37..................................................................................97 xii

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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 SYNTHESIS AND CHARACTERIZATION OF LANTHANIDE COMPLEXES FOR USE IN NEAR-INFRARED LIGHT EMITTING DIODES By Alison Steele Knefely December 2005 Chair: James M. Boncella Major Department: Chemistry The synthesis and characterization of a series of new lanthanide porphyrin and phthalocyanine complexes was investigated in order to study the luminescence properties of these complexes for polymer light emitting diodes. These lanthanide complexes consist of the near-infrared emitting lanthanides (Ln=Pr 3+ Nd 3+ Ho 3+ Tm 3+ Yb 3+ ), a macrocyclic chromophore to sensitize the emission of the lanthanide ion, and a capping ligand to encapsulate and shield the lanthanide from solvent molecules that affect emission efficiency. Lanthanide complexes were synthesized with a variety of chromophores and capping ligands to study the effects of different molecules on device efficiency. The procedure to synthesize LnTPP(X)(DME) complexes provided a high yielding approach to new lanthanide porphyrin complexes that serve as the starting material for a variety of lanthanide-porphyrin complexes via a salt metathesis reaction, replacing the halide and solvent molecules with multidentate ancillary ligands. Lanthanide xiii

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monoporphyrinate complexes, LnTPP (TPP=tetraphenylporphyrin) were synthesized and characterized with the capping ligands hydrotris(pyrazolyl)borate (Tp), (cyclopentadienyl)tris(diethylphosphinito)cobalt(I), K(LOEt), and (hydroxy)quinolate (Q) to study the effects of capping ligands on device efficiency. Effects of varying the chromophore were also studied with the synthesis of lanthanide complexes of tetra(2,3,4-trimethoxyphenyl)porphyrin (TmPP), tetra(4-pyridyl)porphyrin (TPyP), tetra(3-ethylhexyloxypheny)porphyrin (TPPoeh) and phthalocyanine (Pc). These complexes were isolated in high yields and characterized by 1-D and 2-D NMR spectroscopy, UV/Vis spectroscopy and elemental anaylsis. Photoluminescent studies on Ln(porphyrin)L complexes showed NIR emission with quantum efficiencies ranging from 4.1%-0.91%. Electroluminescent studies using devices blended with polystyrene and Ln(porphyrin)L complexes produced NIR emission with quantum efficiencies ranging from 0.01%0.03%. Studies were then conducted on the effects of incorporating the Ln-porphyrin complex into a polymer backbone. A ytterbium-vinylporphyrin complex was copolymerized with t-butylstyrene and trifluoroethyl methacrylate to give a copolymer with 1 mol% of the lanthanide complex and a weight average molecular weight (M w ) and a number average molecular weight (M n ) of ~ 200,000 and 90,000, respectively. Polymers containing trispyrazole borate (Tp) units were synthesized by Prof. Frieder Jaekles group, at Rutgers University, and yielded the Yb-TPP incorporated polymer. Absorption and NIR emission studies showed typical LnTPP absorption and Yb-emission. xiv

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CHAPTER 1 INTRODUCTION Organic and polymeric light emitting diodes (OLEDs and PLEDs) represent a rapidly growing field as industry and academia pursue the development of new, inexpensive, durable, flexible and efficient light sources. These materials are able to produce light through electroluminescence, a process in which an applied electric field generates an excited species that radiatively decays. Research has developed OLEDs and PLEDs that produce light across the entire visible region with device efficiency, brightness and lifetime rapidly approaching commercial target figures (Figure 1.1). 1 NONONOAlNONCCNNNEuOOCF3S3400nm500nm600nm700nm Figure 1.1: Examples of compounds used as emitters in OLEDs. 2 1

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2 The first efficient electroluminescence from an organic solid was demonstrated in the early 1960s using anthracene crystals. 3 Crystals 1-5 mm thick emitted blue light with quantum efficiencies ~ 8%, but with operating voltages between 50-1000 V. 4 Improvement in device construction and operation occurred in 1987 with the construction of the first vacuum deposited multi-layer device. 5 The device consisted of a double layer of organic thin film, with one layer capable of only monopolar transport and the other layer capable of luminescence. Devices using an aromatic diamine as the first organic layer and 8-hydroxyquinoline aluminum (AlQ 3 ) as the luminescent material produced high brightness green light with voltages as low as ~10 V (Figure 1.2). GlassIndium-Tin-Oxide (ITO) anodeDiamineAlq3MgAg cathodeAlNONONOAlq3NNDiamine+Figure 1.2: Configuration of multi-layer device and molecular structures. Since the development of organic thin film electroluminescence by Tang in the 1980s, 6 there has been much interest in organic, as well as conjugated polymer (CP) thin films as new materials for light emitting diodes (LEDs). With the construction of a

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3 device using poly(p-phenylene vinylene), Borroughes et al. showed that polymeric thin films can produce efficient devices. 7 Polymer based LEDs (PLEDs) have many advantages over current inorganic devices such as low costs, easy processing and the ability to emit in wavelengths that span the visible spectrum. 8 The simplest device configuration consists of a single organic/polymeric layer in between an anode and a cathode. With an applied electric field, holes from the anode and electrons from the cathode are driven into the emissive layer, where they recombine to form an excited state of the polymer that decays either radiatively or non-radiatively. The cathode is a low work function material that injects electrons into the lowest unoccupied molecular orbital (LUMO) of the emissive layer and is typically a metal such as calcium, magnesium, or aluminum. The anode is a high work function material that injects holes into the highest occupied molecular orbital (HOMO) of the emissive layer. Indium-tin-oxide (ITO) is a commonly used anode because of its good transmission properties over the desired wavelength range. In a single layer device, the organic/polymeric layer serves as the emitting source as well as the charge carrier and should therefore have high photoluminescence quantum efficiency and the ability to transport holes and electrons. Single layered devices, however, exhibit low quantum efficiencies and short operational lifetimes caused by enhanced quenching at the electrode-organic interface as well as deterioration of the organic layers. 4,9 Because a single material having all the necessary properties for optimal device performance does not exist, additional layers can be added to the LED to improve the charge transport, quantum efficiency of emission and stability of the device. 10 A typical multilayer device is comprised of an anode (ITO), a hole transport

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4 layer, emitting layer, electron transport layer and a cathode (Figure 1.3). More elaborate device construction strategies have also been used. Figure 1.3: Configuration of a typical multi-layer device. An effective hole-transport layer should have a low ionization potential for efficient injection of holes from the anode, a higher exciton energy level than the emissive layer for confining excitons within the emissive layer and should be transparent to the radiation emitted from the device. 10 A commonly used polymer is poly(3,4-ethylenedioxythiophene) doped with polystyrene sulfonic acid (Figure 1.4). The introduction of an electron-transport layer helps control charge injection, transport, and recombination in the emissive layer of the device. The electron transport material should have a high ionization potential to efficiently block holes and high electron mobility to transport electrons to the emissive layer. Oxadiazoles such as 2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxidiazole (PBD) and metal chelates such as AlQ 3 are the most widely used electron transport materials (Figure 1.4). 11 Conjugated polymers (CP) typically used for emission include a yellow-green emitter poly(p-phenylene vinylene) (PPV), the first CP used in a PLED, 7 an orange-red

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5 emitter poly(2-(2-ethylhexyloxy)-5methoxy-1,4-phenylene vinylene) (MEH-PPV) and a blue emitter poly(p-phenylene) derivative, PPP-OR11 (Figure 1.5). SSOOOOSOOn+SO3-SO3HnmPEDOTPSSNNOPBD Figure 1.4: Common organic molecules for hole and electron transport. nPPVMeOOnOO3OO3nMEH-PPVPPP-OR11 Figure 1.5: Commonly used conjugated polymers for emission in device construction. While there has been much research devoted to the improvement of the luminescence and efficiencies of PLEDs, there are some inherent problems with pure PLEDs. When recombination occurs, the spin wave function (S) of the excited molecule

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6 can either be a singlet (S=0) or triplet (S=1). In organic materials, the triplet state decays non-radiatively. 1 Statistically, 75% of injected charges are in the triplet state, limiting organic device efficiencies to about 25%. 10 Another problem is that CPs have broad emission spectra, with a typical full width at half max of 50-200 nm, 12 which gives rise to poor color purity. Consequently, PLEDs do not have the ability to produce finely tuned emission with maximum efficiencies. In order to combat these problems of pure PLEDs, recent work has focused on blending polymers with materials with significant spin-orbit coupling, which facilitates inter-system crossing and allows triplet state emission. Organometallic compounds have been found to be prime examples of good triplet state emitters and therefore successful dopants for polymer devices. The dopant can harvest energy from the polymer by Frster energy transfer (induced dipole mechanism) or Dexter energy transfer (an electron exchange mechanism) (Figure 1.6) or direct charge trapping and exciton formation on the dopant itself. 2,13 Efficient energy transfer from host to dopant depends on the quantum yield of emission by the donor (D*), the light absorbing ability of the acceptor (A) and the overlap of the emission spectrum of D* and the absorption spectrum of A. D*ADA*ADexter Energy TransferForster Energy TransferD* Figure 1.6: Scheme of Dexter and Forster energy transfer mechanisms. Recently published reports show that devices constructed with blends of platinum (Pt) and iridium (Ir) complexes have high luminescence effieciences with the ability to

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7 tune the emission color through much of the visible region by simply changing the ligands of the complex. 1 Thompson and coworkers have synthesized a series of Ir-(acetylacetonate) complexes that give green, yellow and red electroluminescence with external quantum efficiencies ranging from 6%-12% (Figure 1.7). 14 OOIrN2ppy2Ir(acac)G r eenOOIrSN2bt2Ir(acac)YellowOOIrSN2btp2Ir(acac)Red Figure 1.7: Ir(acac) dopants for OLEDs. With unique optical properties such as line like emission, long luminescence lifetimes and a wide spectral range (from blue to near-infrared), the trivalent lanthanides have also been used as dopants in LEDs. 15 The optical properties are governed by the 4f-orbitals, which are shielded from external forces by the 5p and 5s orbitals. The 4f-orbials only weakly interact with the ligands bound to the metal center, leading to small ligand field splitting and thus sharp emission spectra at certain wavelengths regardless of the ligand. The f-f transitions, however, are forbidden and consequently the lanthanides have rather low molar absorptivity coefficients and must be sensitized to produce intense emission. The process of sensitized emission, 16 known as the antenna effect, begins with the ligand absorbing energy, undergoing inter-system crossing from singlet to triplet state

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8 and then transferring the energy to the lanthanide metal center (Figure 1.8). The excited state of the antenna must, therefore, be higher in energy than the emissive level of the lanthanide metal center. absorptionligandLnLn*luminescenceS1T1S0ISC Figure 1.8: Energy transfer from chromophore to lanthanide metal center for sensitized emission. The first reports of devices using lanthanide complexes as the emitting species used Eu(thenoyltrifluoroacetonate) 3 (Eu(TTFA) 3 ) and Tb(acac) 3 to produce red and green emission, respectively. 17,18 Since these reports, there have been many studies examining a variety of Tm 3+ complexes for blue light 19 and Eu 3+ and Tb 3+ complexes for sharp emission of red, green and white light. 10,20-23 Interest in NIR/IR emitting devices for such uses as telecommunication and sensors has brought the blending of CPs with lanthanides to the attention of many research groups including ours. Figure 1.9 shows the normalized luminescence spectra of the near-infrared emitting lanthanides.

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9 Figure 1.9: Normalized luminescence of Yb 3+ Nd 3+ Er 3+ Ho 3+ and Tm 3+ 24 Recent reports show NIR emission from devices made with blends of a CP and Er (acetylacetonato) 3 (1,10-phenanthroline) to give 1.54 m emission 25 and a Nd(lissamine) complex to produce typical Nd 3+ luminescence at 890, 1060 and 1340 nm. 26 The low lying radiative levels of the lanthanide ions are easily quenched by the vibrational energy of O-H and C-H molecules from solvents or ligands; thus, ligands bound to the lanthanides should not only contain a chromphore that can readily excite the lanthanide, but should also encapsulate the ion to shield it from solvent molecules. In efforts to improve device luminescence and efficiencies, our group has become interested in synthesizing lanthanide complexes of nitrogen-based macrocycles for use in NIR LEDs. The following chapters discuss the synthesis and characterization of a series of new lanthanide porphyrin and phthalocyanine complexes. The use of these compounds in

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10 PLED devices and the characterization of the performance of these devices are also presented.

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CHAPTER 2 LANTHANIDE TETRAPHENYLPORPHYRIN COMPLEXES: SYNTHESIS, CHARACTERIZATION AND LUMINESCENCE STUDIES Introduction Porphyrins are interesting molecules because their large systems give them properties that allow them to be used in photodynamic therapy, areas of light harvesting, catalysis and optics. 27 As highly conjugated molecules, porphyrins are promising organic molecules for the design of efficient luminescent materials. Forrest et al. have used tetraphenylporphyrin (TPP) as the red emitter in light emitting diodes (LED), 28,29 while other groups have examined platinum porphyrin complexes as emissive dopants in LEDs. 12,29-32 The small absorption coefficients of the lanthanides make light absorption and emission an inefficient process for these metal ions and require that sensitization by a coordinating ligand be used for efficient light absorption and emission. Contributing factors to the luminescence intensity are the intensity of the ligand absorption and the efficiency of ligand-to-metal energy transfer. 33 With a molar absorptivity ~300,000 and triplet energies typically around 12,000 cm -1 -17,000 cm -1 studies show that TPP efficiently absorbs light and transfers energy to the metal ions. 34-36 These studies also reveal that lanthanide-porphyrin complexes possess rapid rates of energy transfer from the porphyrin to the lanthanide ion. The intense Soret band of lanthanide porphyrin complexes leads to facile singlet excitation, while the presence of the lanthanide ion gives rise to facile inter-system 11

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12 crossing to the low energy triplet state that can readily excite the emissive states of the lanathanide ion. 37-39 Meanwhile, the highly delocalized system of these complexes is suitable for efficient hole-transport 40,41 through the bulk material. This combination of properties makes TPP a proficient ligand for energy transfer to near-infrared emitting lanthanide ion. Previous Synthetic Procedures The first synthesis of lanthanide-monotetraphenylporphyrin (LnTPP) complexes was reported by Wong et al. in 1974. 42 Lanthanide-monoporphyrinate complexes have been studied for their use as NMR shift reagents, 42-44 and as probes in the area of clinical and molecular biology, 45,46 but difficulties in their syntheses have stunted the growth of research in this field. As the accepted LnTPP synthesis, Wongs procedure involves the reaction between Ln(acac) 3 and the free base tetraphenylporphyrin (H 2 TPP) in refluxing trichlorobenzene. While progress of the reaction monitored by UV/Vis spectroscopy shows a yield of greater than 90%, the LnTPP(acac) compound is isolated by column chromatography, leading to product decomposition and isolated yields of 10-30%. With the use of this method, Yband Er-porphyrin complexes were synthesized and found to be viable as NIR lumophores in NIR LEDs. 39 These results stimulated our interest in finding a high yielding synthetic procedure that would allow us to access complexes with a variety of ligands that might have improved luminescent properties. Since the first reported synthetic procedure for lanthanide monoporphyrinate complexes, there have been few reports of new procedures that improve conditions or yields with most research utilizing Wongs procedure. 37,47-49 In 1999, an alternate procedure generating a hydrated LnTPP(Cl) complex was published. 50 The disadvantage

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13 of this synthetic procedure is that the complexes are coordinated to several equivalents of water. Since the excited state of the lanthanide ion is effectively quenched by vibrational energy transfer to solvents or ligands containing O-H groups, this synthetic procedure is not amenable for use in near IR emissive systems. Recently our lab has developed a high yielding synthetic procedure for lanthanide tetraphenylporphyrin chloride complexes 51 via a salt metathesis reaction between tetraphenylporphyrin dianion and anhydrous LnCl 3 Reaction of these compounds in refluxing toluene gave the lanthanide tetraphenylporphyrin chloride (LnTPPCl(DME)) in yields greater than 75%. Progress of the reaction can be monitored by UV/Vis spectrometry as the Soret band shifts from 417 nm of free TPP to 422 nm for metalloporphyrin. The complexes are then easily isolated by simple filtration and recrystallization. This synthetic approach was successfully applied to ytterbium, thulium, erbium and holmium complexes (Figure 2.1). NNNN2Li(DME)2+LnCl3Toluenereflux, 4hNNNNLnClOOLn= Ho, Er, Tm, Yb Figure 2.1: Synthesis of LnTPPCl(DME) where Ln = Ho, Er, Tm, and Yb. These complexes were then used to synthesize a series of sterically saturated monoporphyrinate lanthanide complexes via a second salt metathesis reaction, replacing the chloride ion and solvent molecule with an ancillary ligand (Figure 2.2). Addition of

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14 potassium acetylacetonate to the Yb complex in dimethoxyethane gave the YbTPP(acac) complex in yields greater than 90%. NNNNPhPhPhPhLnClOOCoPPPEtOOOEtOEtOEtOEtOEtOONNNNPhPhPhPhLnrt, 12hTHFK(LOEt),NNNNNNBHKTp,DMErt, 12hNNNNPhPhPhPhLnLn = Ho, Er, Tm, Yb Figure 2.2: Synthesis of LnTPP(L) complexes (Ln= Ho, Er, Tm,Yb and L= Tp,L(OEt)). Synthesis of Nd and Pr Complexes In order to complete the series of near-IR emitting lanthanides, the same synthetic routes used to synthesize LnTPPCl(DME) complexes of the smaller lanthanides Er, Ho, Tm, and Yb were used to try to make the complexes of the larger lanthanides, neodymium (Nd) and praseodymium (Pr). After four hours of refluxing the LnCl 3 with the TPP anion in dry toluene, the UV/Vis spectrum of the reaction mixture showed free TPP with an absorbance peak at 415 nm and no evidence of metallated porphyrin. The reaction was then refluxed for twelve hours with the same results and no isolation of product. Half-Sandwich Complexes Inspired by the recent work of the Bianconi group, 52 we attempted another synthetic route to obtain Nd and Pr porphyrin compounds. Bianconi recently reported the synthesis of neodymium tris(1-pyrazolyl)borate diiode (NdTpI 2 (THF) 2 ), and we pursued

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15 the displacement of the iodide ligands with TPP dianion as an alternative route to the desired complexes, NdTPPTp and PrTPPTp. NdCl3(THF)3KTpTHFNNNNNNNdBHTHFTHFClClrt, 12h Figure 2.3: Synthesis of NdTpCl 2 (THF) 2 In an attempt to make the analogous chloride complex, NdTpCl 2 (THF) 2 NdCl 3 (THF) 3 was treated with KTp (Figure 2.3). After stirring for twelve hours, the resulting blue solution was filtered, the solvent removed under reduced pressure and the product was extracted with methylene chloride. Layering the CH 2 Cl 2 solution with pentane gave an immediate blue precipitate, which had proton NMR shifts corresponding to the Tp protons at -0.55 ppm, 7.64 ppm and 13.2 ppm. The proton NMR, however, was significantly different from the proton NMR of the diiodide complex in that the Tp peaks had different chemical shifts and there were no peaks associated with coordinated THF. The Biaconi group reported 52 the synthesis of ytterium Tp chloride and bromide complexes, but only the iodide complex of neodymium. These results suggested that perhaps the chloride ions were not large enough to satisfy the coordination sphere of neodymium and the complex was not a half sandwich but perhaps a dimer or higher aggregate. Attempts to obtain crystals of this compound were unsuccessful.

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16 LnTPPI(DME) Complexes Given the differences in the behavior of the chloride and iodide complexes, the complexes NdI 3 (THF) 4 (1) and PrI 3 (THF) 4 (2) were prepared according to the literature procedure used for CeI 3 (THF) 4 as shown in equation 2.1. 53 Ln0+3CH3CH2ITHFLnI3(THF)n (2-1) The lanthanide triiodide complexes 1 and 2 were used in salt metathesis reactions with Li 2 TPP(DME) 2 (Figure 2.4). After refluxing the lanthanide triiodide and TPP dianion in toluene for four hours, the UV/Vis of the reaction mixture showed an absorption at ~425 nm corresponding to metallated TPP. The solution was then separated from KI by hot filtration and after layering with pentane, the complexes NdTPPI(DME) (3) and PrTPPI(DME) (4) precipitated in 74% and 72% yields, respectively. NNNN2Li(DME)2+LnI3Toluenereflux, 4hNNNNLnIOOLn = Nd, Pr Figure 2.4: Synthesis of 3 and 4. In order to study the phosphorescence of TPP in our devices, we synthesized gadolinium and lutetium porphyrin complexes whose metal centered excited states are too high in energy to be sensitized by TPP. Similar to the previously stated procedure, GdTPPCl(DME) (5) and LuTPPCl(DME) (6) were synthesized by reaction of the lanthanide trichloride with the dilithiated TPP compound.

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17 Single crystals of NdTPP(I)(THF) 2 were grown by slow diffusion of pentane into a saturated solution of THF and were analyzed by X-ray crystallography. The thermal ellipsoid plot of the solidstate structure of the neodymium complex with selected atom labels is shown in figure 2.5. The crystal structure shows that the lanthanide ion is seven coordinate with the metal ion bonded to the four nitrogens of the porphyrin ring, one iodide and two oxygens from coordinating THF molecules. The metal ion is too large to fit into the porphyrin cavity and so the porphyrin ring adopts a domed conformation to maximize the Ln-N interactions. The average Nd-N bond length is 2.436(1) and the Nd atom sits 1.286(6) above the mean plane of the coordinating nitrogens on the porphyrin ring. Single crystals of LuTPPCl(DME) (6) suitable for X-ray structure determination were grown from a saturated solution of CH 2 Cl 2 layered with pentane. The thermal ellipsoid plot of the solidstate structure of the lutetium complex with selected atom labels is also shown in figure 2.4. Similar to the Nd complex, the LuTPPCl(DME) complex is seven coordinate with the metal ion bonded to the four nitrogens of the porphyrin ring, as well as one chloride ion and two oxygens from the coordinating DME molecule. The ionic radius of the Lu ion is about 0.15 smaller than the Nd ion, giving rise to shorter averaged metal-ligand bond distances. The average Lu-N bond length is 2.306(1) and the Lu ion sits 1.098(0) above the mean plane defined by the nitrogen atoms of the porphyrin ring.

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18 Figure 2.5: Thermal ellipsoid plots of the molecular structure of NdTPPI(DME) (top) and LuTPPCl(DME) (6) (bottom), showing selected atom labels, drawn at the 50 % probability level. The hydrogen atoms have been excluded for clarity. LnTPP(L) Complexes The LnTPPX(DME) compounds have been used to synthesize a series of sterically saturated monoporphyrin lanthanide complexes via a second salt metathesis reaction, replacing the halide and solvent molecule with a mutlidentate, monoanionic ancillary ligand. The low-lying emissive levels of these lanthanide ions are easily quenched by molecular vibrations, especially O-H and C-H oscillators. 54-56 In order to enhance the

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19 luminescence properties of the complex, the ancillary ligand must provide enough steric bulk to prevent quenching agents such as water from interacting with the metal. Furthermore, the polydentate, monoanionic axial ligand saturates the coordination sphere of the metal center while maintaining a neutral complex. The complexes that we have used to fill the remaining coordination sites of the metal are hydrotris (pyrazolyl) borate (Tp), (cyclopentadienyl)tris(diethylphosphinito)cobalt (K(LOEt)), and (hydroxy)quinolate (Q) ligands. LnTPP(Tp) complexes Similar to cyclopentadienide ligands, Tp ligands are one of the most common supporting ligands in transition metal and lanthanide chemistry, 57 with the first lanthanide-polypyrazolylborate complex published by Bagnall in the 1970s. 58 The binding of the monoanionic ligand occurs in a tridentate fashion with the nitrogens of the pyrazolyl binding to the lanthanide. The binding properties of this ligand are easily tuned by simple manipulation of the 3and 5-substituents of the pyrazolyl rings. Synthesis of LnTp complexes is a simple salt metathesis reaction involving a lanthanide halide or triflate and the potassium or sodium salt of the ligand to give a mono-, bis-, or tris-ligand complexes, depending on the steric bulk of the ligand. The LnTPP(Tp) complexes of holmium, erbium, thulium and ytterbium were synthesized previously by Foley. 51,59 Recently Wong et al. published another synthetic route for the NdTPP(Tp) complex, prepared by reaction of the Ln(Porphyrin)(H 2 O) 3 Cl with KTp. 60 The analogous praseodymium, neodymium, 59 gadolinium and lutetium complexes were synthesized by reaction of the potassium salt of Tp (KTp) with LnTPPX(DME) (where X = I for Pr and Nd and X = Cl for Gd and Lu) in DME giving the desired LnTPPTp (Figure 2.6). The reaction was performed under an inert

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20 atmosphere to prevent the hydrolysis of the LnTPP bonds. After stirring at room temperature for twelve hours, the products were extracted with CH 2 Cl 2 and were then isolated as purple crystalline solids in high yields by recrystallization from a mixture of CH 2 Cl 2 and pentane. The purity of the bulk material was confirmed by elemental analyses and the molecular structure of NdTPPTp (7) was determined by X-ray crystallography. NNNNPhPhPhPhLnXOO+NNNNNNBHKTpDMErt, 12hNNNNPhPhPhPhLnLn = Pr, Nd, Gd, Lu Figure 2.6: Synthesis of LnTPP(Tp) where Ln = Pr, Nd, Gd, Lu. Slow diffusion of pentane into a saturated CH 2 Cl 2 solution gave X-ray diffraction quality crystals of NdTPPTp (7) (Figure 2.7). The coordination geometry of the metal ion is best described as a distorted capped trigonal prism with the trigonal prism being composed of three of the porphyrin N atoms and the three pyrazolyl N atoms with the capping group being the final porphyrin N atom. The distortion in the structure is due to the different bond lengths between Nd and the nitrogens atoms of the porphyrin group.

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21 The distances of Nd-N(4) and Nd-N(1), which are 2.458 and 2.447 respectively, are slightly longer than the Nd bond between N(2) and N(3), which are 2.427 and 2.421 respectively. The center of the Nd atom is 1.302(4) above the center of the mean plane defined by the pyrrole nitrogens of the porphyrin and 1.891(7) below the mean plane defined by the pyrazolyl nitrogen plane. The pyrrole rings deviate from the mean plane defined by the pyrrole nitrogens by 17.0, 8.9, 15.3 and 5.1 for the rings containing N(1), N(2), N(3) and N(4) respectively. The porphyrin becomes puckered in order to accommodate the large metal, causing these deviations from the mean plane. Figure 2.7: Thermal ellipsoid plot of NdTPPTp (7) showing selected atom labels drawn at the 50 % probability level. The hydrogen atoms have been excluded for clarity. LnTPP(LOEt) complexes The tripodal ligand [(C 5 H 5 )Co{P(O)(OEt) 2 } 3 ] was first reported in 1974 61 by Klaui and has been shown to be a versatile compound in the synthesis of heterobimetallic complexes. Coordination occurs through the oxygen atoms to form a tridentate ligand that has been demonstrated by Klaui et al. to form stable coordination compounds with

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22 many metal ions including lanthanide ions. 62 Edelmann et al. have recently reported the first organolanthanide-LOEt complex by reaction of [( 8 -C 8 H 8 )Sm(-Cl)(THF)] 2 with Na(LOEt) to obtain ( 8 -C 8 H 8 )Sm(LOEt). 63 The synthetic procedure for preparing LnTPP(LOEt) is similar to that used for the TP complexes. The synthesis and crystal structure of the ErTPP(LOEt) and YbTPP(LOEt) complexes have been reported by Wong et al. 64,65 This procedure, however takes 48 hours and the desired products must be isolated and purified by column chromatography. The procedure developed by our lab synthesizes the same product in a one pot, 12 hour reaction in DME using simple recrystallization techniques to isolate LnTPP(LOEt) (Ln= Ho, Er, Tm, Yb) in high yields. 59 The LOEt complexes of Nd and Pr were synthesized using THF as the solvent. The reaction of K(LOEt) and NdTPPI(DME) in DME led to low yields, with the proton NMR spectrum showing free ligand (Figure 2.8). NNNNPhPhPhPhLnIOO+CoPPPEtOOOEtOEtOEtOEtOEtOONNNNPhPhPhPhLnrt, 12hTHFK(LOEt) Figure 2.8: Synthesis of LnTPP(LOEt), where Ln = Nd (11), Pr (12).

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23 LnTPP(quinolate) complexes Whether used as an emitting layer or an electron transport layer, tris-(8-hydroxyquinoline)aluminum (AlQ 3 ) is one of the most frequently used materials for organic light emitting devices. 66,67 The incorporation of this known electron transporter into blends of our lanthanide porphyrin complexes resulted in a significant increase in device efficiency. 38 AlQ 3 likely increases the electron transport properties of the material, thereby improving the charge carrier balance in the devices. Inspired by this work, we synthesized a lanthanide porphyrin complex with quinolate capping ligands The procedure for the synthesis of the YbTPP(Q)THF (13) complex was analogous to the TP and LOEt procedures. The potassium salt of quinlone (KQ) was added to YbTPPCl(DME) in THF under an inert atmosphere for twelve hours to give the desired product (Figure 2.9). NNNNPhPhPhPhYbClOO+NNNNPhPhPhPhYbrt, 12hTHFKQNOO Figure 2.9: Synthesis of YbTPP(Q)THF (13). Crystals suitable for X-ray diffraction were grown from THF solutions of the complex layered with pentane. The crystal structure of 13 (figure 2.10) illustrates that the

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24 complex is a monomer with a coordination number of seven around the metal center. The ytterbium sits 1.102(5) above the plane of the porphyrin and has an average Yb-N bond distance of 2.331(3) The bond distances on the ligand are 2.180(2) and 2.538(3) for Yb-O(1) and Yb-N(5), respectively. The quinolate ligand is not bulky enough to shield the lanthanide from solvent coordination as seen by the coordinating THF molecule with a bond distance of 2.397(3) for Yb-O(2). Figure 2.10: Thermal ellipsoid plot of YbTPP(Q)THF (13) showing selected atom labels drawn at the 50 % probability level. The hydrogen atoms have been excluded for clarity. NMR Studies In this section, the proton 1-D and 2-D NMR spectroscopy results will be discussed. Despite their paramagnetic nature, lanthanide complexes can give NMR spectra having narrow line widths with large spectral windows due to the nature of the f-electron paramagnetism. 43,68 The paramagnetic shifts are dependent on the electronic structure of the lanthanide ion as well as the position of the resonating nuclei with respect

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25 to the metal. Because of the uncertainty of the paramagnetic shifts of these new compounds, the proton peaks cannot be assigned as easily as in diamagnetic materials. However, the use of the relative integrals as well as simple 2-D NMR experiments has allowed us to do a complete assignment of the proton NMR spectra of these compounds. NdTPPTp The 1-D proton NMR spectrum of 7 is shown in figure 2.11. Assuming the rotation of the phenyl rings on the porphyrin is slow compared to the time scale of the experiment, 68,69 there should be nine proton peaks. Of these nine peaks, five of the peaks correspond to the protons from the phenyl rings and have an integration of four, three of the peaks correspond to the Tp protons and have an integration of three and the ninth peak corresponds to the pyrrole protons and has an integration of eight. (The B-H proton of the Tp group is almost never observed, even in diamagnetic compounds, due to quadrapolar broadening from the boron atom). The spectrum, however, only shows eight peaks with integrated ratios (labeled A-H) of 3:4:8:7:4:4:3. Studies have shown that paramagnetic complexes have a significant temperature dependence of their resonance shifts. 43 Lauffer et al. showed that with lanthanide complexes of diethylenetriaminepentaacetate, overlapping singlets at room temperature can be observed at low temperatures. 70 Variable temperature NMR studies (Figure 2.12) in the range of 20 to 50 C show that peak D splits into two peaks, D a and D b with relative integrations of 4 and 3 respectively. Using the integrals, peaks A, D b and H are assigned to the Tp protons while peaks B, D a E, F and G are assigned to the protons on the phenyl ring and peak C is assigned to the protons on the pyrrole.

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26 NNNNNNBHNNNNPhPhPhNdABCDaEFGHDb Figure 2.11: 1 H NMR of NdTPPTp (7). By running a COSY NMR experiment, we were able to observe the proton couplings that are obscured by the line width in the 1-D NMR spectrum. By looking at the reference peaks along the horizontal or vertical axes and their cross peaks off the diagonal, the proton-proton correlations are seen and used in peak assignment. The 2-D spectra of 7 (figure 2.13) show a cross peak between peaks A and D b with no other couplings, confirming the Tp assignment of these two protons.

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27 Figure 2.12: Variable temperature NMR of the phenyl region of NdTPPTp (7) from 20-50. Because of its proximity to the paramagnetic nucleus the relaxation time of peak H is too fast to allow the appearance of the crosspeaks between H and either D b or A in the NMR spectrum. So, peak H is assigned the proton nearest the metal because it is shifted significantly upfield and, with a half width of 22.4 Hz, it is the broadest Tp peak. The expanded area of the COSY spectrum (figure 2.13) shows correlations between peaks B and D a D a and E, E and F, and F and G. Because of their correlations with only peaks D a and F respectively, peaks B and G are assigned the ortho protons on the phenyl ring. The half width of peak G is 15.6 Hz while the half width of peak B is 15.0 Hz, so G is assigned to the proton pointing towards the metal and Tp. The rest of the assignments were made using the same logic, with peak F being the meta proton pointing towards the metal and D a pointing away and E being the para proton.

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28 Figure 2.13: Full COSY NMR of NdTPPTp (7) (top), expansion from 8.5-5.5 ppm (bottom).

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29 NdTPP(LOEt) One and two-dimensional NMR experiments were used to analyze the LOEt complexes as well. The 1-D proton NMR spectrum (figure 2.14) shows nine peaks for NdTPP(LOEt) (11). Similar to the analysis of 7, the peaks can be assigned to protons via their relative integrations. Starting with peak A at 10.16 ppm, the integrated ratios are 5:4:8:4:4:4:12:18. There is one peak with an integration of 5, which is expected for the Cp protons, two peaks with integrations of 12 and 18,which are the methylene and methyl protons on the LOEt ligand respectively, and then there are the expected number of peaks and integrations for the phenyl and pyrrole protons. The COSY spectra of NdTPP(LOEt) (11) (figures 2.15 and 2.16) show that peaks H and I are coupled to each other, supporting the ethoxy group assignment. While not observed in the 1-D NMR, the 2-D NMR spectrum shows the inequivalence of the diastereotopic protons on the methylene group. Looking at the expanded region, the cross peaks show that peaks B and G are the ortho protons, C and F are the meta protons and peak E is the para proton. Because peak G is broader than peak B, it is assigned the ortho proton closest to neodymium. The half widths of G and B were 25.3 Hz and 24.1 Hz, respectively.

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30 CoPPPEtOOOEtOOEtOEtOEtOONNNNPhPhPhNdH,IJABCDEFG Figure 2.14: 1 H NMR spectrum of NdTPP(LOEt) (11).

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31 Figure 2.15: COSY NMR of NdTPP(LOEt) (11). Figure 2.16: COSY NMR of NdTPP(LOEt) (11), expansion from 8-2ppm.

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32 LnTPP(L) Photoluminescence and Electroluminescene Studies After the syntheses and full characterization of the LnTPP(L) complexes, the photoluminescence (PL) and electroluminescence (EL) properties of these compounds were examined. Recent work 39 has shown that formulation of the EL device materials can be guided by PL studies. Due to the lengthy process of device construction, PL studies were carried out on blends of polymer and the lanthanide complexes to determine if the complexes would be luminescent. PL studies on NdTPPTp, performed by Ben Harrison, showed NIR emission around 900 nm, 1069 nm and 1300 nm, which are the 4 F 3/2 4 I 9/2 4 I 11/2 and 4 I 13/2 transitions of Nd (figure 2.17). The quantum efficiency ( em ) was determined to be 2.4 %. 59 PL studies of NdTPP(LOEt) had similar results (figure 2.17). 59 Reported quantum efficiencies of other Nd-complexes range from 0.4 % 71 to 1.0 %. 72 Figure 2.17: PL emission NdTPPL (solid lines, L = Tp, dashed lines, L = LOEt). PL studies of the Pr complexes showed no NIR luminescence and therefore no devices were made with these complexes. Lack of emission is not surprising in that the

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33 energy states that are below the 3 of the TPP ligand are closely spaced (separations of 2000-4000 cm -1 ), causing nonradiative decay to be efficient. 59 The device construction is shown in figure 2.18. The hole transport layer, PEDOT-PSS, was spin coated onto ITO covered glass, followed by the active layer (consisting of the lanthanide complex blended with polystyrene (PS)) and then finally the calcium layer as well as a layer of aluminum to prevent oxidation of the calcium. While most of the device construction used the conjugated polymer, PPP-OR11, 73 our labs have demonstrated the fabrication of NIR-LEDs using blends of our lanthanide porphyrin complexes in non-conjugated host polymers, where the porphyrin serves as not only the charge carrier but also luminescent material (figure 2.19). 73,74 Figure 2.18: Device architecture.

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34 Figure 2.19: Charge hopping cartoon. Devices made with blends of NdTPP(LOEt) and PS (2:1 weight ratio, complex:polymer) turned on at about 4 V and were able to operate efficiently at 9 V, producing NIR emission around 900 nm, 1069 nm and 1300 nm, which are the 4 F 3/2 4 I 9/2 4 I 11/2 and 4 I 13/2 transitions of Nd (figure 2.20). 74 Figure 2.20: Electroluminescence emission of Ln(TPP)(LOEt) in polystyrene measured at 9 V. Ln = Nd (solid line), Yb (dashed line) and Er (dotted line). 74

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35 The quantum efficiency of blends with YbTPPTP, polystyrene and the known electron transporter, 8-hydroxyquinoline aluminum (AlQ 3 ) is ten times higher than devices without AlQ 3 Through these studies, we have found that LnTPP(L) is more efficient in the transport of holes and, therefore, creates a charge imbalance and low device efficiencies. There have been many studies on the poor ability of lanthanides to transport charge carriers, especially electrons. 21,75,76 With hopes of improved charge balance, PL and EL studies of YbTPP(Q)THF (13) were conducted by Garry Cunningham. PL studies showed NIR emission with a predominant peak ~ 980 nm. The quantum efficiency was calculated to be 0.0091 in CH 2 Cl 2 which is significantly lower than efficiencies found for our other YbTPPL complexes. 59 Devices made with 13 emitted ~970 nm with a quantum efficiency of 0.00002-0.00004, depending on device loading of the complex. Again, these efficiencies are found to be lower than efficiencies previously reported for YbTPPL complexes. 73 As seen in the crystral structure of 13, the capping ligand does not complete the coordination sphere of Yb and is not sterically hindering enough to prevent solvents, such as THF, from coordinating to the complex. It is likely that the proximity of the C-H bonds in the coordinated THF molecules provides efficient pathways for nonradiative decay, thus lowering the quantum efficiency of the complex. Summary and Conclusions In summary, novel neodymium and praseodymium complexes of tetraphenylporphyrin have been synthesized, thus completing the series of NIR emitting lanthanide porphyrin complexes. Through a simple salt metathesis reaction with the corresponding triiodides and dilithioTPP complexes, LnTPPI(DME) of Nd and Pr complexes were cleanly isolated in good yields. Analogous compounds of gadolinium

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36 and lutetium were synthesized in the same fashion. From these starting materials, the lanthanide compounds were easily complexed with a number of ancillary ligands including Tp, LOEt and quinolate. These compounds have been fully characterized through crystallography, proton and COSY NMR studies, with proton peak assignment accomplished by integration of the 1-D proton spectrum and from proton correlations observed in the 2-D spectrum. Recent work has demonstrated that devices do not require conjugated polymers and that blends of the lanthanide complexes with nonconjugated polymers produce NIR emission. PL studies found that devices blended with Nd complexes give NIR emission with a quantum efficiency of about 0.0024, while Pr complexes do not emit in the NIR. The NdTPPL complexes produce NIR emission with quantum efficiencies higher than published reports, supporting the design of emitting Ln complex consisting of the porphyrin sensitizing molecule and ancillary capping ligand. PL and EL studies carried out with blends of NdTPP(L) and PS show that the TPP complex acts as the charge carrier that is more efficient in hole transport. Synthesis of the YbTPPQ was an attempt to balance the charge transfer in the emissive layer. However, the capping ligand is not sterically encumbering enough to hinder solvent coordination, facilitating nonradiative decay pathways and lowering device efficiency. Experimental Materials and Reagents Unless otherwise stated, all syntheses were carried out on a double manifold Schlenk line under an atmosphere of nitrogen or in a N 2 filled glovebox. Glassware was oven dried prior to use. Methylene chloride, dimethoxyethane, chloroform and dimethlyforamide were purchased from Fisher Scientific and were dried with an

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37 appropriate drying agent. 77 Pentane, tetrahydrofuran and toluene were purchased from Aldrich Chemicals and dried by passing through a column of activated alumina. Following dehydration, all solvents were degassed and stored over 4 molecular sieves in resealable ampoules with fitted Teflon valves. 8-hydroxyquinoline was purchased from Aldrich and used as received. The complexes (Cyclopentadienyl)tris(diethylphospinito)cobalt(I) (LOEt), 78 hydridotris(1-pyrazolyl)borate (Tp H ), 79 TPNdCl 2 THF, 52 (LOEt)NdCl 2 THF, 52 TPP, 80 Li 2 TPP, 81 and YbTPPCl(DME) 51 were synthesized following literature procedures. Potassium 8-hydroxyquinoline (KQ) was synthesized by reacting 8-hydroxyquinoline with potassium hydride in THF. Elemental analyses were performed at the University of California, Berkley, Micro-Mass Facility or University of Florida Spectroscopic Services. Proton NMR spectra were measured at 300 MHz at room temperature, unless otherwise stated and on Varian Gemini 300, VXR 300, Mercury 300 or Bruker 300 NMR machines. Chemical shifts were referenced to residual solvent peaks and are reported relative tetramethylsilane. The spectral window was also different for each metal complex and was determined by expanding the window until peak positions remained unchanged. COSY spectra were run using the standard parameters of the instrument. All UV/VIS spectra were run in 1 cm path length quartz cuvettes in CH 3 Cl unless stated otherwise. The samples were prepared and run under N 2 on a double-beam Cary-100 UV-visible spectrometer. Synthesis NdI 3 (THF) 4 (1) In a round bottom flask equipped with a side arm, Nd metal (4.98 g, 0.0346 mol) was washed with dry THF (3 x 30 mL). Dried and degassed ethyliodide (22 ml, 0.27

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38 mol) was then added along with 30 mL of THF. After refluxing under N 2 for 20 hours, the brown solution was cooled and the THF removed in vacuo. Soxhelt extraction of the brown solid was performed in ca. 100 mL of THF under N 2 for 3 days. Following the completion of the extraction, the THF was removed, giving 1 as a blue solid in 46% yield (13 g, 0.016 mol). PrI 3 (THF) 4 (2) Using the same procedure for 1, Pr metal (2.97 g, 0.0211 mol) and CH 3 CH 2 I (13.1 ml, 0.169 mol) were refluxed under N 2 in dry THF (30 mL) giving 2 as yellow solid in 38% yield (6.1 g, 0.0075 mol). NdTPPI(DME) (3) NdI 3 (THF) 4 (0.51 g, .61 mmol) and Li 2 TPP(DME) (0.499 g, 0.615 mmol) were added together in the dry box. About 40 mL of dry toluene was then added and the purple solution was refluxed under N 2 The reaction was followed by UV/VIS spectrometry (a peak at 425 nm with no peaks at ~415 nm indicated completion). After refluxing for four hours, the solution was filtered while hot via cannula. The residue was then washed with CH 3 Cl (2 x 20 mL) and the toluene and CH 3 Cl solutions were combined and reduced in volume to 10 mL. The solution was then layered with ca. 20 mL of pentane. After 12 hours, the solution was filtered, leaving a red/purple solid (0.443 g, 0.455 mmol) in 74% yield. 1 H NMR (300 MHz, CD 2 Cl 2 ): 8.95( 1/2 = 5.78 Hz, 8H, H-pyrrole), 8.12( 1/2 = 17.33 Hz, 4H, o-C 6 H 5 TPP), 7.56 ( 1/2 = 19.32 Hz, 4H, m-C 6 H 5 TPP), 7.31 ( 1/2 = 5.71 Hz, 4H, p-C 6 H 5 TPP), 6.92 ( 1/2 = 19.49 Hz, 4H, m-C 6 H 5 TPP) 4.90 ( 1/2 = 18.72 Hz, 4H, o-C 6 H 5 TPP), -5.42 ( 1/2 = 217 Hz, 10H, DME). UV/VIS (CH 2 Cl 2 ) max (log ): 422 (5.45), 514(3.95), 552(4.37), 590(3.95) nm. Anal. Calcd. for C 48 H 38 N 4 NdIO 2 : C, 59.19; H, 3.93; N, 5.75. Found: C, 57.31; H, 4.02, N, 5.52.

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39 PrTPPI(DME) (4) In the same fashion as 3, PrTPPI(DME) was synthesized by refluxing PrI 3 (THF) 4 (0.5 g, 0.1 mmol) and Li 2 TPP (0.501 g, 0.108 mmol) in ca. 30 mL of toluene for four hours. The purple solid was isolated in 74% yield (0.44g, .451mmol). 1 H NMR (300 MHz, CDCl3): 7.73 ( 1/2 = 16.19 Hz, 4H, o-C 6 H 5 TPP)), 6.81( 1/2 = 18.66 Hz, 4H, m-C 6 H 5 TPP), 6.29 ( 1/2 = 5.07 Hz, 4H, p-C 6 H 5 TPP,), 5.53 ( 1/2 = 5.7 Hz, 8H, H-pyrrole), 5.33( 1/2 = 18.79 Hz, 4H, m-C 6 H 5 TPP) 0.78 ( 1/2 = 17.79 Hz, 4H, o-C 6 H 5 TPP). UV/VIS (CH 2 Cl 2 ) max (log ): 424 (5.45), 514(3.95), 552(4.37), 590(3.95) nm. Anal. Calcd. for C 48 H 38 N 4 PrIO 2 : C, 59.39; H, 3.92; N, 5.77. Found: C, 58.99; H, 3.96; N,5.84. GdTPP(Cl)DME (5) In the glove box, Li 2 TPP(DME) (0.75 g, 0.80 mmol) and GdCl 3 (0.22 g, 0.80 mmol) were added to a Schlenk flask. Dry toluene (ca. 30ml) was then added and the green/blue solution was refluxed under N 2 for 3 hours, over time the color changed to red. After refluxing, the solution was removed in vacuo and the compound extracted with CHCl 3 (3 x 30 mL). The chloroform solution was reduced to ca. 20 mL and then layered with hexane (30 mL) to give purple crystalline material in 55% yield (0.4 g, 0.5 mmol). UV/VIS (CH 2 Cl 2 ) max (log ): 425(5.46), 514(4.47), 552(4.87) nm. Anal. Calc. for C 48 H 38 N 4 GdClO 2 : C, 64.23; H, 4.25; N, 6.25. Found: C,65.06; H, 4.12; N, 6.12. LuTPP(Cl)DME (6) In the same fashion of 5, LuTPPCl(DME) was synthesized by refluxing LuCl 3 (0.51 g, 1.7 mmol) and Li 2 TPP(DME) (1.58 g, 1.77 mmol) in ca. 30 mL of toluene for 3 hours. After the color change of the solution from green/blue to red, the solution was removed in vacuo and the compound was extracted with CH 2 Cl 2 (3 x 30 mL) and filtered. The CH 2 Cl 2 solution was reduced in volume to ca. 20 mL and then layered with hexane

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40 (30 mL) to give purple crystalline material in 63% yield (0.99 g, 1.09 mmol). 1 H NMR (C 6 D 6 ): 9.09(s, 8H), 8.47(m, 4H), 8.07(m, 4H), 7.57(m, 12H). UV/VIS (CH 2 Cl 2 ) max (log ): 420(4.80), 510(3.75), 548(3.961), 585(3.57) nm. Anal. Calc. for C 48 H 38 N 4 LuClO 2 : C, 63.13; H, 4.16; N, 6.14. Found: C, 59.49; H, 3.78; N, 5.71. NdTPPTp (7) To a solution of 3 (0.15 g, 0.15 mmol) in dry DME (30 mL), was added KTP (0.041 g, 0.15 mmol). The reaction mixture was left to stir for twelve hours at room temperature. The solution was removed in vacuo and the purple compound was extracted with ca. 30 mL of CH 2 Cl 2 leaving a white residue of KI. The volume of the red/purple solution was reduced to 10 mL and then layered with pentane (10 mL). After being cooled to 0 C for 12 hours, the solution was filtered, leaving a purple solid. The mother liquor was reduced in volume (ca.10 mL) to allow more product to precipitate. Recrystallization of the combined solids from CH 2 Cl 2 /pentane gave X-ray quality crystals in 64% yield (0.093 g, 0.096 mmol). 1 H NMR (C 6 D 6 ): 14.65( 1/2 = 5.61 Hz, 3H, H-Tp), 7.97( 1/2 = 15.05 Hz, 4H, o-C 6 H 5 Tpp), 7.82( 1/2 = 4.25 Hz, 8H, H-pyrrole), 6.93( 1/2 = 5.08 Hz, 7H, m-C 6 H 5 Tpp, H-Tp), 6.47( 1/2 = 3.25 Hz, 4H, p-C 6 H 5 Tpp), 5.75( 1/2 = 16.88 Hz, 4H, m-C 6 H 5 Tpp), 2.88( 1/2 = 15.66 Hz, 4H, o-C 6 H 5 Tpp), 6.23( 1/2 = 22.41 Hz, 3H, H-Tp). UV/VIS (CH 3 Cl), max (log ) = 425(5.29), 555(4.36) nm. Anal Calc. for C 53 H 38 BN 10 Nd: C, 65.76; H, 3.93; N, 14.47. Found: C, 65.67; H, 3.96; N, 14.33. PrTPPTp (8) Following the same procedure for 7, 4 (0.150 g, 0.155 mmol) and KTP (0.041 g, 0.15 mmol) were stirred together in dry DME (30 mL) for twelve hours at room

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41 temperature. After recrystallization from CH 2 Cl 2 /pentane, 49% (0.073 g, 0.076 mmol) of product was collected. 1 H NMR (C 6 D 6 ): 18.08( 1/2 = 4.89 Hz, 3H, H-Tp), 8.13( 1/2 = 14.81 Hz, 4H, o-C 6 H 5 Tpp), 6.63( 1/2 = 5.09 Hz, 7H, m-C 6 H 5 Tpp, H-Tp), 5.90( 1/2 = 3.97 Hz, 4H, p-C 6 H 5 Tpp), 5.36( 1/2 = 3.69 Hz, 8H, H-pyrrole), 4.64( 1/2 = 17.51 Hz, 4H, m-C 6 H 5 Tpp), -0.47( 1/2 = 14.09 Hz, 4H, o-C 6 H 5 Tpp), -13.87( 1/2 = 11.23 Hz, 3H, H-Tp). UV/VIS (CH 3 Cl), max (log ) = 424(5.30), 516(3.78), 555(4.34), 592(3.84) nm. Anal. Calc. for C 53 H 38 BN 10 Pr: C, 65.86; H, 3.93; N, 14.50. Found: C, 66.30; H, 3.91; N, 14.23. GdTPPTp (9) Following the procedure used to synthesize NdTPPTp, KTp (0.067 g, 0.26 mmol) was added to a solution of GdTPPCl(DME) (0.24 g, 0.26 mmol) in toluene (ca. 20 mL). The reaction was stirred overnight at room temperature. The purple solution was removed in vacuo and the crude material was extracted with CH 2 Cl 2 (ca. 30 mL). The solution was filtered and layered with pentane (ca. 30 mL) to give the product in 55% yield (0.14 g, 0.14 mmol). UV/VIS (CH 2 Cl 2 ), max (log ) = 424(5.72), 513(4.33), 552(4.57), 590(4.33) nm. Anal. Calc. for C 53 H 38 BN 10 Gd: C, 64.76; H, 3.86; N, 14.25. Found: C, 64.63; H, 3.71; N, 12.99. LuTPPTp (10) In the same manner as GdTPPTp, LuTPPCl(DME) (0.1 g, 0.10 mmol) and KTP (0.027 g, 0.109 mmol) were mixed in toluene for twelve hours. After recrystalization from CH 2 Cl 2 /pentane, 60% (0.059g, 0.06mmol) yield was recovered. 1 H NMR (C 6 D 6 ): 8.98(s, 8H), 8.29(m, 4H), 7.79(m, 4H), 7.43(m, 12H), 6.38(s, 4H), =5.53(s, 3H), 5.25(s, 3H). UV/VIS (CH 2 Cl 2 ), max (log ) = 421(5.12), 513(4.67), 550(4.93), 588(4.66)

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42 nm. Anal. Calc. for C 53 H 38 BN 10 Lu: C, 63.61; H, 3.80; N, 14.00. Found: C, 63.43; H, 3.51; N, 13.91. NdTPP(LOEt) (11) To a stirring solution of 3 (0.125 g, 0.128 mmol) in dry THF (30 mL) was added K(LOEt) (0.075 g, 0.125 mmol). The purple solution was stirred for twelve hours at room temperature. The solvent was then removed in vacuo and the product was extracted into 30 mL of toluene. The volume of toluene was reduced to about 10 mL and layered with ca. 10 mL of pentane. After 24 hours at 0 C, the purple precipitate was isolated by filtration and recrystallized from CH 2 Cl 2 /pentane. The crystals were washed with pentane (3 x 10 mL) to give 11 in 30% yield (0.05 g, 0.04 mmol). 1 H NMR(C 6 D 6 ): 10.13( 1/2 = 3.28 Hz, 5H, H-Cp), 7.98( 1/2 = 19.35 Hz, 4H, o-C 6 H 5 Tpp), 6.80( 1/2 = 20.88 Hz, 4H, m-C 6 H 5 Tpp), 6.53( 1/2 = 4.32 Hz, 8H, H-pyrrole), 6.35( 1/2 = 3.22 Hz, 4H, p-C 6 H 5 Tpp), 5.61( 1/2 = 20.32 Hz, 4H, m-C 6 H 5 Tpp), 2.02( 1/2 = 20.63 Hz, 4H, o-C 6 H 5 Tpp), -0.26( 1/2 = 47.23 Hz, 12H, -OCH 2 CH 3 ), -0.83( 1/2 = 11.27, 18H, OCH 2 CH 3 ). UV/VIS (CH 3 Cl), max (log ) = 427(5.42), 518(3.93), 560(4.30), 599(3.97) nm. Anal. Calc. for C 61 H 63 CoN 4 O 9 P 3 Nd: C, 56.83; H, 4.69; N, 4.35. Found: C, 55.13; H, 4.81; N, 3.90. PrTPP(LOEt) (12) The same procedure as 11 was used. PrTPPI(DME) (0.2 g, 0.2 mmol) and K(LOEt) (0.121 g, 0.206 mmol) were reacted to give 12 in 30% yield (0.08g, 0.062mmol). 1 H NMR (C 6 D 6 ): 14.92( 1/2 = 1.79 Hz, 5H, H-Cp), 7.96( 1/2 = 23.50 Hz, 4H, o-C 6 H 5 Tpp), 6.28( 1/2 = 26.26 Hz, 4H, m-C 6 H 5 Tpp), 5.45( 1/2 = 3.21 Hz, 4H, p-C 6 H 5 Tpp), 3.96( 1/2 = 26.20 Hz, 4H, m-C 6 H 5 Tpp), 3.04( 1/2 = 2.47 Hz, 8H, H-pyrrole), -2.16( 1/2 = 13.98

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43 Hz, 18H,-OCH 2 CH 3 ), -2.39( 1/2 = 30.25 Hz, 6H, -OCH 2 CH 3 ), -2.59( 1/2 = 27.79 Hz, 6H, -OCH 2 CH 3 ), -3.02( 1/2 = 25.20 Hz, 4H, o-C 6 H 5 Tpp). UV/VIS (CH 3 Cl), max (log ) = 425(5.14), 520(3.90), 559(4.35), 600(4.03) nm. Anal Calc. for C 61 H 63 CoN 4 O 9 P 3 Pr: C, 56.93; H, 4.78; N, 4.33. Found: C, 55.73; H, 4.96; N, 3.84. YbTppQ(THF) (13) In the glove box, K(8-hydroxyquinolate) (KQ) (0.02 g, 0.01 mmol) was added to a solution of YbTPPCl(DME) (0.1 g, 0.01 mmol) in THF (30 mL) and stirred for 12 hours. The solvent was removed under reduced pressure and the resultant solid was extracted with CH 2 Cl 2 (3 x 30 mL). The solution was reduced to ca. 10 mL and layered with ca. 20 mL of pentane, giving 13 as a purple crystalline solid (0.08 g, 57%). Crystals suitable for single crystal X-ray diffraction studies were grown from a saturated solution of THF (10 mL) that was layered with pentane (20 mL). UV/VIS (CH 2 Cl 2 ) max (log ): 422 (5.43), 512 (3.93), 552 (4.26), 589 (3.95) nm. Anal. Calc. for C 57 H 42 N 5 O 2 Yb: C, 68.21; H, 4.19; N, 6.90. Found: C, 67.48; H, 4.45; N, 6.97. X-ray NdTPPI(THF) 2 Data were collected at 173 K on a Siemens SMART PLATFORM equipped with A CCD area detector and a graphite monochromator utilizing MoK radiation ( = 0.71073 ). Cell parameters were refined using up to 8192 reflections. A full sphere of data (1850 frames) was collected using the -scan method (0.3 frame width). The first 50 frames were remeasured at the end of data collection to monitor instrument and crystal stability (maximum correction on I was < 1 %). Absorption corrections by integration were applied based on measured indexed crystal faces.

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44 The structure was solved by the Direct Methods in SHELXTL5, and refined using full-matrix least squares. The non-H atoms were treated anisotropically, whereas the hydrogen atoms were calculated in ideal positions and were riding on their respective carbon atoms. The asymmetric unit consists on the complex and a disordered thf molecule. The THF molecule could not be modeled properly, thus program SQUEEZE, a part of the PLATON package of crystallographic software, was used to calculate the solvent disorder area and remove its contribution to the overall intensity data. The complex has its iodine and two THF ligands disordered about a 2-fold rotation axis perpendicular to the plane of the macrocycle but only the Iodine atom of the minor part could be seen due to its small site occupation factor (refined to 5% then fixed in the final cycles of refinement). A total of 548 parameters were refined in the final cycle of refinement using 21110 reflections with I > 2(I) to yield R 1 and wR 2 of 4.06% and 10.31%, respectively. Refinement was done using F 2 LuTPPCl(DME) The crystal was mounted in a nylon cryoloop from Paratone-N oil under argon gas flow. The data were collected on a Bruker SMART APEX II charge-coupled-device (CCD) diffractometer, with KRYO-FLEX liquid nitrogen vapor cooling device. The instrument was equipped with graphite monochromatized MoK X-ray source (= 0.71073 ), with MonoCap X-ray source optics. A hemisphere of data was collected using scans, with 5-second frame exposures and 0.3 frame widths. Data collection and initial indexing and cell refinement were handled using APEX II software. Frame integration, including Lorentz-polarization corrections, and final cell parameter calculations were carried out using SAINT+ software. The data were corrected for

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45 absorption using the SADABS program. Decay of reflection intensity was monitored via analysis of redundant frames. The structure was solved using Direct methods and difference Fourier techniques. All hydrogen atom positions were idealized, and rode on the atom they were attached to. The final refinement included anisotropic temperature factors on all non-hydrogen atoms. Structure solution, refinement, graphics, and creation of publication materials were performed using SHELXTL. NdTPPTP Data were collected at 173 K on a Siemens SMART PLATFORM equipped with A CCD area detector and a graphite monochromator utilizing MoK radiation ( = 0.71073 ). Cell parameters were refined using up to 8192 reflections. A full sphere of data (1381 frames) was collected using the -scan method (0.3 frame width). The first 50 frames were remeasured at the end of data collection to monitor instrument and crystal stability (maximum correction on I was < 1 %). Absorption corrections by integration were applied based on measured indexed crystal faces. The structure was solved by Direct Methods in SHELXTL5, and refined using full-matrix least squares. The non-H atoms were treated anisotropically, whereas the hydrogen atoms were calculated in ideal positions and were riding on their respective carbon atoms. The asymmetric unit consists of two complexes and a pentane molecule disordered over a center of inversion. The disorder is resolved where only the methyl groups are disordered. A total of 1208 parameters were refined in the final cycle of refinement using 12451 reflections with I > 2(I) to yield R 1 and wR 2 of 3.69% and 6.42%, respectively. Refinement was done using F 2

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46 YbTppQ(THF) Data were collected at 173 K on a Siemens SMART PLATFORM equipped with A CCD area detector and a graphite monochromator utilizing MoK radiation ( = 0.71073 ). Cell parameters were refined using up to 8192 reflections. A full sphere of data (1850 frames) was collected using the -scan method (0.3 frame width). The first 50 frames were remeasured at the end of data collection to monitor instrument and crystal stability (maximum correction on I was < 1 %). Absorption corrections by integration were applied based on measured indexed crystal faces. The structure was solved by the Direct Methods in SHELXTL5, and refined using full-matrix least squares. The non-H atoms were treated anisotropically, whereas the hydrogen atoms were calculated in ideal positions and were riding on their respective carbon atoms. Atoms C56 and C57 of the coordinated thf were disordered and were refined isotropically in two parts, second part being C56 and C57. The asymmetric unit consists of the complex, an uncoordinated thf and a pentane molecule. The THF and pentane molecules were disordered and could not be modeled properly, thus program SQUEEZE, a part of the PLATON package of crystallographic software, was used to calculate the solvent disorder area and remove its contribution to the overall intensity data. A total of 585 parameters were refined in the final cycle of refinement using 24756 reflections with I > 2(I) to yield R 1 and wR 2 of 3.98% and 9.20%, respectively. Refinement was done using F

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CHAPTER 3 LANTHANIDE SUBSTITUTED TETRA(ARYL)PORPHYRIN AND PHTHALOCYANINE COMPLEXES : SYNTHESIS, CHARACTERIZATION AND LUMINESCENCE STUDIES We have demonstrated that devices produce NIR emission when made with blends of the lanthanide porphyrin complexes in non-conjugated host polymers such as polystyrene. In these devices the porphyrin complex must serve as the charge carrier. These studies have also demonstrated that LnTPP is more efficient in the transport of holes and, therefore, creates a charge imbalance in the active layer of the device. This imbalance leads to charge recombination outside the active layer and thus low device efficiencies. In order to enhance device performance, we must enhance the charge balance in our active layer by enhancing the electron transport. In this chapter, the synthesis and characterization of substituted lanthanide-porphyrin and phthalocyanine complexes will be discussed as will the effect of the substituents on device efficiency. Substituted Tetra(aryl)porphyrins Much work has been done with studying the substituent effects on the redox properties of substituted tetraphenylporphyrins. 82,83 These studies found that electron-withdrawing and electron-donating groups affect the reduction and oxidation potentials of the porphyrins as well as the rate of electron transfer. Kadish et al. found that when electron-withdrawing substituients were placed on the phenyl rings of TPP, reductions were easier and oxidations were more difficult. 83 Korovin et al. 84 studied the effects of porphyrins with different aromatic substituents on the luminescence of ytterbium compounds. They reported that the quantum yields of porphyrins with pyridine or 47

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48 quinoline meso-subsituents are higher than in the case of phenyl substituents. By incorporating methoxy, alkoxy and pyridyl groups into our porphyrin complexes, we sought to study the effects of both electron donating and withdrawing groups on our device efficiency. The goal was to indentify a lanthanide complex that would promote balanced injection, transport and recombination of charge carriers. Synthesis The synthesis of the ytterbium monoporphyrinate complexes began with the reaction of the dilithiated porphyrins with Yb(Cl) 3 (THF) 3 under anhydrous, oxygen free conditions to give the metallated porphyrin (Figure 3.1). 51 The Yb(porphyrin)Cl complexes, YbTmPP(Cl)DME (14), YbTPPoeh(Cl)DME (19), and YbTPyP(Cl)DME (22) were then allowed to react with the potassium salt of the desired axial ligand to give the final products Yb(TmPP)Tp (15), Yb(TPPoeh)Tp (20) and Yb(TPyP)L(OEt) 3 (23), (Figure 3.2). 85 NNNNRRRR2Li(DME)NNNNRRRRYbClOOToluene(DMF)R=NOMeOMeOMeO,,141922YbCl3(THF)3 Figure 3.1: Synthesis of YbTmPP(Cl)DME (14), YbTPPoeh(Cl)DME (19), and YbTPyP(Cl)DME (22).

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49 The reaction to metallate the substituted porphyrin ligands with ytterbium proceeded smoothly via nucleophilic displacement of chloride from YbCl 3 Differences in the solubility of the reactants and products necessitated differences in the reported procedures. For example, the TpyP compounds were found to be insoluble in most solvents and the syntheses of these compounds were carried out in dry DMF. After stirring Li 2 TpyP(DMF) (21) with Yb(Cl 3 )(THF) 3 in DMF at reflux to give YbTPyPCl(DMF), the solution was removed in vacuo and the crude material washed several times with DME to remove any soluble impurities. Addition of the axial ligand, LOEt, alleviated the solubility issues of the TpyP compounds. Once the halide was replaced with LOEt, the compound was cleanly isolated in high yields by fractional recrystallization from CH 2 Cl 2 On the other hand, the TPPeoh complexes were found to be extremely soluble in most organic solvents, including pentane. These compounds were isolated as oils by extracting the residues of the reactions with pentane and subsequent solvent removal under reduced pressure.

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50 YbClOOYbCoPPPOOEtOEtOEtOOEtEtOOEtOYbNNNNNNBHK(LOEt)KTpNNNNNNNNNNNNRRRRNNNNRRRROMeOMeOMeO,R=231520 Figure 3.2: Synthesis of Yb(TmPP)Tp (15), Yb(TPPoeh)Tp (20) and Yb(TPyP)L(OEt) 3 (23). NMR Studies The complexes were characterized by proton NMR, UV/VIS spectroscopy as well as by elemental analysis. Uncertainty about the magnitude of the contact and pseudocontact shift in these new paramagnetic compounds adds difficulty to assigning the NMR peaks, but using the relative integration of the peaks and what we have learned from similar structures 85 facilitated assignment of the spectra. The proton NMR spectra of YbTmPP(Cl)DME (14) and Yb(TPyP)L(OEt) 3 (23) are shown in figures 3.3 and 3.4, respectively. Assuming that rotation of the phenyl rings on the porphyrin ligand is slow on the NMR timescale, 68,85 compound 14 should have eight peaks. Of the eight, three correspond to the methoxy groups on the phenyl ring and have an integration of 12 each, two with a relative integral of 4 each correspond to the protons on the phenyl rings, two with relative integrals of 6 and 4, correspond to the coordinated DME and one with an integration of 8 is assigned to the pyrrole protons on the porphyrin. Using these

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51 integrations, peaks A and C were assigned to the protons on the phenyl ring, peaks D, E and F were assigned to the methoxy groups on the phenyl ring while the remaining peaks, G and H, arise from the coordinated DME. Similar to the analysis of compound 14, the proton peaks in the NMR spectrum of 23 were assigned to protons via their relative integrations. Of the nine peaks, two are the diasteriotopic protons of the methylene on the L(OEt) ligand and have integrations of 6, one with an integration of 18 represents the methyl protons on the ligand, one with an integration of 5 is the Cp ring. There are four peaks assigned to the pyridyl ring and one to the pyrrole with integrations of 4 and 1, respectively (Figure 3.4). Figure 3.3: Proton NMR spectrum of Yb(TmPP)Cl(DME) (14) in DMSO-d 6 (*).

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52 Figure 3.4: Proton NMR of Yb(TPyP)L(OEt) 3 (23) in C 6 D 6 ( denotes silicon grease impurity). Electrochemistry Cyclic voltammetry is a useful technique for electrochemical studies of new systems and provides valuable information on rates of oxidations/reductions as well as the HOMO/LUMO band gap of the compound. While CH 2 Cl 2 for example, is a common solvent used in organic electrochemistry, it can only be used for potentials as high 1.8 V and as low as .9 V vs. Ag/Ag + Ionic liquids, on the other hand allow a much wider potential window for electrochemical studies. Furthermore, these solvents have the added advantage of not requiring a supporting electrolyte since they are inherently strong ionic conductors. 86,87

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53 The electrochemical characterization studies of the lanthanide-porphyrin complexes along with their free base porphyrins were performed in the ionic liquid, 1-Butyl-1-methyl-pyrrolidium bis(trifluoromethyl)sulfonamide ([BMP + ]-[NTF ]) (Figure 3.5) in order to increase the available potential window (Figure 3.6). Electrochemical investigations were performed in a three-electrode cell with a platinum counter wire, platinum working disk and silver wire pseudo-reference electrode. Additionally, ferrocene (Fc) was used as an internal reference standard. The insolubility of compound Yb(TPPoeh)Tp (20) in [BMP + ]-[NTF ] prevented the study of its electrochemistry. N+NSSOOOOFFFFFFFigure 3.5: 1-Butyl-1-methyl-pyrrolidium bis(trifluoromethyl)sulfonamide ([BMP + ]-[NTF ]), ionic liquid used for electrochemical studies. Figure 3.6: Cyclic voltamogram of [BMP + ]-[NTF ]. A cyclic voltammogram is characterized by several important parameters. These observables include the peak currents (i pa and i pc ) and the corresponding peak potentials

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54 (E pa and E pc ) and provide the basis for analyzing the cyclic voltammetric response. A typical reduction process is expressed as: O+ne-RnIf R nis easily oxidized back to O upon reversing the direction of the potential scan, the process is said to be Nernstian reversible, giving the characteristic current versus potential plot seen in figure 3.7. From a CV, the potentials at which redox reactions occur, the reversablilty and stability of the oxidized and reduced species as well as the HOMO/LUMO band gaps can be determined. Under ideal conditions, for a mass-transport limited reversible process the peak potential separation (E pa E pc ) is equal to 59/n mV (at 25 C) for all scan rates, the peak current ratio (i pa /i pc ) is equal to 1 for all scan rates and the peak current function increases linearly as a function of the square root of the scan rate. The average of E pa and E pc gives E 1/2 of the redox waves. The band gap is thus the difference between the first oxidation/reduction wave and the E 1/2 of the first reduction/oxidation wave. Figure 3.7: CV of a reversible reduction and reoxidation. Previously reported cyclic voltammograms of LnTPP(acac) complexes consisted of two oxidation waves with E 1/2 of 0.7 and 0.9 V and two reduction waves with E 1/2 of

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55 .32 and .68 V (vs. SCE). 47 Those waves correspond to four reversible one-electron transfer process, with the electrode mechanism shown in figure 3.8. LnTPP(acac)e-LnTPP(acac)-LnTPP(acac)2-LnTPP(acac)+LnTPP(acac)2+e-e-eFigure 3.8: Electrode reaction mechanism of LnTPP(acac). The cyclic voltammogram of TmPP in [BMP + ]-[NTF ] at a scan rate of 0.1 V/s is shown in figure 3.9. The first reduction/oxidation wave, peak B is reversible with a i pc /i pa equal to one and E pa E pc equal to 79 mV (under the conditions, the peak potential difference is equal to 110 mV for the Fc/Fc + coupling, a well established completely reversible process). The E 1/2 for TmPP were determined to be .54 V and .78 V for the two reduction waves and 0.66 V for the oxidation wave. The band gap is 2.2 eV. C B A Figure 3.9: CV of TmPP in ionic liquid with a scan rate of 0.1 V/s ( indicates Fc/Fc + ).

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56 Figure 3.10 shows a similar cyclic voltammogram of the complex YbTmPPTp (15) in [BMP + ]-[NTF ] at a scan rate of 0.3 V/s. Similar to LnTPP(acac) complexes, there are two reduction waves, however there is only one oxidation wave. The first reduction/oxidation wave, peak B is reversible with a i pc /i pa equal to one and E pa E pc equal to 250 mV (under the conditions, the peak potential difference is equal to 260 mV for the Fc/Fc + coupling, a well established completely reversible process). Compared to YbTPP(acac) with E 1/2 of .76V and 0.28 V (vs. Fc/Fc + ) for the first reduction and oxidation, respectively, the E 1/2 for complex 15 were determined to be .52 V and .97 V for the two reduction waves and 0.68 V for the oxidation wave. The band gap is 2.2 eV. C B A Figure 3.10: Cyclic voltammogram of 15 in ionic liquid with a scan rate of 0.3 V/s ( indicates Fc/Fc + ). The cyclic voltammogram of the free base porphyrin, TPyP is shown in figure 3.11.

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57 Figure 3.11: Cyclic voltammogram of TPyP in ionic liquid with a scan rate of 0.3 V/s. There is one irreversible reduction/oxidation peak with E 1/2 determined to be .62 V. There is also one irreversible oxidation/reduction peak and the E 1/2 was determined to be 0.71 V. The cyclic voltammogram of the reduction and the oxidation for YbTPyP(LOEt) (23) is in figure 3.12. In the reduction half, there are two reduction/oxidation waves, A and B. Peak A is reversible with i pc /i pa equal to one and E pa E pc equal to 85 mV (under the conditions, the peak potential difference is equal to 131 mV for the Fc/Fc + coupling). There are no reversible oxidation waves present, however, there are several poorly resvolved irreversible waves at 0.22 V and 0.85 V. The E 1/2 were determined to be .69 V and .12 V for the two reduction wave. The band gap is 1.9 eV.

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58 B A Figure 3.12: Cyclic voltammogram of the oxidation (left) and reduction (right) ofYbTPyP(LOEt) in ionic liquid with a scan rate of 0.3 V/s. The cyclic voltammogram of YbTPPTp is in figure 3.13. There are two oxidation/reduction waves, A and B, and two reduction/oxidation waves, C and D, which are quasi reversible. The E 1/2 were determined to be .53 V and .91 V for the two reduction waves and 0.51 V for the oxidation wave. The band gap is 2.0 eV. D C B A Figure 3.13: Cyclic voltammogram of YbTPPTp in ionic liquid with a scan rate of 0.2 V/s ( indicates Fc/Fc + ).

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59 Figure 3.14 shows the cyclic voltammogram of the complex YbTPP(LOEt) in [BMP + ]-[NTF ]. Similar to LnTPP(acac) complexes, there are two reduction waves and two oxidation waves. The oxidation /reduction waves, peaks A and B are reversible with E pa E pc equal to 75 and 68 mV, respectively (under the conditions, the peak potential difference is equal to 75mV for the Fc/Fc + coupling, a well established completely reversible process). Peaks C and D are quasi reversible and peak E is irreversible. The E 1/2 for complex YbTPP(LOEt) were determined to be .79 V for the first reduction wave and 0.35 V for the first oxidation wave. The band gap is 2.2 eV. D C B A E Figure 3.14: Cyclic voltammogram ofYbTPP(LOEt) in ionic liquid with a scan rate of 0.05 V/s ( indicates Fc/Fc + ).

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60 Table 3.1 shows the half wave potentials and the band gap determined by the electrochemical studies of the lanthanide complexes and the corresponding free base porphyrins. When compared to TmPP, the redox potentials of 15 are quite similar, suggesting that reductions are occurring on the macrocycle and addition of the metal ion and Tp does not affect the electrochemistry. When comparing 15 to other Ln-porphyrin complexes such as YbTPPTp, YbTPP(LOEt) and YbTPP(acac) the oxidation reaction is not reversible and occurs at a higher potential, suggesting that substituents may destablize the oxidation products. Similar to 15, the oxidation and reduction of 23 are affected by the substituent. Comparing 23 with YbTPP(LOEt),reduction of the complex occurs at a lower potential while the oxidation process is irreversible. Comparing YbTPP(L) with different capping ligands also shows changes in the reduction and oxidation potentials. Reported results show that the CV of YbTPP(acac) has two reversible reduction and two reversible oxidation reactions. Complex YbTPP(Tp) has two reduction and two oxidation reactions, which occur at higher potentials and are not reversible. Complex YbTPP(LOEt) has two reduction and two reversible oxidation waves as well as another oxidation peak, which irreversible.

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61 Table 3.1: Half wave potentials and band gaps of Ln-porphyrin complexes (potentials are reported vs Fc/Fc + internal standard) a Irreversible peak and so was determined by E p Complex Red, E 1/2 (v) 1 2 Ox, E 1/2 (v) 1 2 Eg (eV) TmPP -1.54 -1.78 0.66 2.6 Yb(TmPP)Tp (15) -1.52 -1.97 0.68 2.2 TPyP -1.62 0.71 2.3 YbTPyP(LOEt) (23) -1.69 -2.12 0.22 a 1.9 TPP (ionic liquid) -1.78 0.51 2.3 YbTPP(Tp) -1.53 -1.92 0.51 2.0 YbTPP(LOEt) -1.79 -2.31 0.35 0.7 2.1 YbTPP(acac) 47 -1.76 0.28 2.0 TPP in CH 2 Cl 2 83 -1.64 -1.99 0.58 0.83 2.02 ZnTPP in CH 2 Cl 2 83 -1.76 -2.15 0.34 0.65 2.1 Photoluminescence and Electroluminescene Studies After the synthesis and full characterization of the substituted ytterbium porphyrin complexes, the photoluminescence (PL) and electroluminescence (EL) properties of these compounds were examined. The photoluminescence studies by Garry Cunnigham showed photoluminescence from the metal-based f-states ( 2 F 5/2 2 F 7/2 ) with efficiencies ranging from 0.9% for YbTPPQ to 4.1% for YbTmPPTp. With the exception of YbTPPQ, PL efficiencies were similar to other YbTPP complexes and higher than other reported Yb-complexes, with efficiencies reported in the range of 0.1% 88 to 0.8%. 72 The emission spectral properties for all of the porphyrin complexes were nearly identical,

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62 with emission maxima at ~980 and ~1020 nm, similar to the previous YbTPP complexes studied. Light emitting diodes containing blends of the substituted Yb-porphyrin complexes and polystyrene were prepared. The configuration of all devices tested was ITO/PEDOT-PSS/PS-porphyrin complex/Ca;Al 40:100:5:200 (nm). Intensity / arb. units Wavelength / nm 85090095010001050 Figure 3.15: Electroluminescence of Yb(TMPP)TP (bottom), Yb(TPyP)L(OEt) 3 (middle), and Yb(TPPoeh)TP (top) as a function of increasing voltage, starting at 6 V to 20 V. Electroluminescence spectra of devices containing a 2:3 wt. ratio (complex:polymer) of the porphyrin complexes dispersed in polystyrene show the ~980 nm emission of the Yb 3+ 2 F 5/2 2 F 7/2 transition as also seen in the PL measurements with a weaker peak at ~920 nm which is attributed to the crystal field splitting of the Yb 3+ f-states by the axial and porphyrin ligands (Figure 3.15). The Yb(TPyP)LOEt devices

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63 were considerably less stable and failed at a lower voltage than devices fabricated from the other porphyrin complexes. The external quantum efficiency for each of the complexes is ~1 x 10 -4 which is similar to devices constructed with Yb(TPP)TP. 73 Summary Lanthanide-porphyrin complexes have been synthesized and characterized with a variety of porphyrin-phenyl ring substituents in order to improve the efficiency of electron transport and consequently the luminescence of our devices. The electrochemistry of these complexes and the free base porphyrins were studied. The lanthanide complexes show a decrease in the reduction/oxidation potentials when compared with the unsubstitued YbTPPTp and YbTPP(LOEt) complexes and there is little interpretable data for the oxidation of YbTPyP(LOEt), suggesting that the substiuents affect the stability of the oxidized complexes. These electrochemical studies also showed that changing the capping ligand affects the electrochemistry of the complexes. PL and EL studies, however, show NIR luminescence with no change in device efficiencies. Because there appears to be no correlation between the electrochemical results and device efficiency suggests that the factors involved in device construction outweigh any differences that arise from the identity of the porphyrin substituents. So, for PL and EL studies, changing the porphyrin-phenyl ring substituents has little effect on the electronic properties of the complex and does little to enhance device efficiency. Lanthanide-Phthalocyanine Complexes Like TPP, phthalocyanine (Pc) (Figure 3.16) is an aromatic tetradentate macrocycle with a strong absorption at ~720 nm. Because of these properties, lanthanide complexes

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64 of Pc were synthesized to investigate their luminescence properties and compare them with the LnTPP complexes. NNNNNNNNHH Figure 3.16: Phthalocyanine (Pc). There are many examples of LnPc 2 sandwich-type complexes in the literature. 89-91 These complexes however, have a strong interligand charge transfer band at 1550 nm that would quench many of the NIR emissions under investigation. 92,93 In order to use Pc as a chromophore for the lanthanides, a convenient synthesis of the monoPc complexes would be desirable. Synthesis and Structure of LnPc(LOEt) Complexes The LnPc complexes were made with a methodology that was similar to that used for the LnTPP complexes. Dilithiophthalocyanine was synthesized by refluxing 1,2 dicyanobenzene and lithium in pentanol. The synthesis of LnPcCl, which is published in the patent literature, 94 consists of refluxing Li 2 Pc with anhydrous LnCl 3 in dry DME. The LnPcCl(DME) complex was then in turn used to synthesize the LnPc(LOEt) complex. This procedure has been used to make the Ho, Er, Tm, and Yb complexes. The synthesis of LnPcTP was attempted, but the product was insoluble in all organic solvents and therefore purification and characterization was not completed.

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65 In order to make NdPcI(DME) (24) and PrPcI(DME) (25), Li 2 Pc was was stirred at reflux with the lanthanide triiodide complex in DME for twelve hours (Figure 3.17). These complexes are insoluble in DME and were isolated by filtration. NNNNNNNNNNNNNNNNLnIOOLnI3 4THFDME+Ln = Nd, Prreflux, 4h2 Li(DME)+-Figure 3.17: Synthesis of LnPcI(DME), Ln= Nd, Pr. The (LOEt) complexes were then synthesized by reaction of LnPcI(DME) with K(LOEt) in THF at room temperature for twelve hours (Figure 3.18). NNNNNNNNLnPcI(DME)+CoPPPOOROROROORROROOKTHFrt, 12hCoPPPOOROROROORROROOLnLn = Nd,PrR = CH2CH3 Figure 3.18: Synthesis of LnPc(LOEt) complexes, Ln = Pr, Nd. The LnPc(LOEt) compounds were recrystallized from CH 2 Cl 2 and pentane and were isolated in high yields and purity. A thermal ellipsoid plot of PrPc(LOEt) (27) is shown in Figure 3.19.

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66 Figure 3.19: Solid state structure of PrPc(LOEt) (27). The complex is located on a mirror plane, which passes through Pr, Co, two N atoms on the Pc ring and C on the Cp ring. This plane, however, does not pass through any of the P atoms on the ligand, but between them causing them to occupy different positions and creating disorder. Due to considerable amount of disorder associated with the three OP(OC 2 H 5 ) 2 groups on the ligand, a drawing was used to model the crystal structure. Bond lengths of Pr-N(2A) and Pr-N(4A) are 2.466(2) and 2.468(2) respectively. The metal sits 1.459(2) above the plane defined by N(2), N(2A), N(4) and N(4A). In order to accommodate the large metal, the rings of N(2) and N(4) become distorted with deviations from the plane of 10.6 and 5.3 respectively. When compared to the crystal structure of YbPc(LOEt), 92 the Pr sits 0.212(2) further from the plane, due to the larger ionic radius of Pr.

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67 NMR Studies As demonstrated with the TPP complexes, one and two-dimensional proton NMR spectra were used to identify the PC complexes. The proton NMR spectrum of PrPc(LOEt) (27) in figure 3.20 has 5 peaks (labeled A-E) with relative integrals of 5:8:8:12:18, respectively. With these relative integrals, the peaks were assigned as peak A corresponding to the Cp protons, peaks B and C to the protons on the Pc ring, and peaks D and E to the methylene and methyl protons on the ethoxy group respectively. There is no separation of the diastereotopic protons of the methylene in the Pr complex. The COSY spectra in figures 3.21 and 3.22 confirm the assignments made, showing one set of cross peaks between peaks B and C and another between peaks D and E, confirming the peak assignments from the 1-D spectra. Figure 3.20: 1 H NMR spectrum of PrPc(LOEt) (27).

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68 Figure 3.21: COSY NMR spectra of PrPc(LOEt) (27). Figure 3.22: Expansion of COSY NMR spectra of PrPc(LOEt) (27). Photoluminescence Studies PL studies were done by Gary Cunningham. Results show that there was no photoluminescence for either the neodymium or the praseodymium complexes. The

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69 triplet state of Pc is ~1050 nm and is too low in energy to sensitize neodymium and praseodymium. Similar results were obtained with Ho-, Tmand YbPc(LOEt) complexes. PL studies of ErPc(LOEt) observe the expected emission ~1500nm, however, the emission was extremely weak and no devices have been fabricated because of the extremely low intensity of this emission. 92 Summary The series of LnPc monomeric complexes was completed with the synthesis of neodymium and praseodymium complexes. These complexes were charactized by 1-D and 2-D NMR spectroscopy and crystallography. Unfortunately, PL studies show no observable luminescence for the Pr-,Nd-Hoand TmPc(LOEt) complexes. Experimental Materials and Reagants Unless otherwise stated, all syntheses were carried out on a double manifold Schlenk line under an atmosphere of nitrogen or in a N 2 filled glovebox. Glassware was oven dried prior to use. Methylene chloride, dimethoxyethane, chloroform and dimethlyforamide were purchased from Fisher Scientific and were dried with an appropriate drying agent. 77 The complexes (Cyclopentadienyl)tris(diethylphospinito)cobalt(I) (LOEt), 78 and hydridotris(1-pyrazolyl)borate (Tp H ) 79 were synthesized according to literature procedure. Tetrapyridylporphyrin (TpyP), pyrrole, 2-ethylhexyl bromide, 3-hydroxybenzaldehyde and 8-hydroxyquinoline were purchased from Aldrich and used as received. Tetra(3,4,5 trimethoxyphenyl) porphyrin (TmPP) was synthesized by the reaction of trimethoxybenzaldehyde and pyrrole in refluxing propionic acid. 95 Lithiated TmPP 81 and PC 92 were prepared using literature procedures. Elemental analyses were performed at

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70 the University of California, Berkley, Micro-Mass Facility or University of Florida Spectroscopic Services. Proton NMR spectra were measured at 300 MHz at room temperature unless otherwise stated, on Varian, Gemini 300, VXR 300, Mercury 300 or Bruker 300 NMR spectrometers. Chemical shifts in spectra were referenced to residual solvent peaks and are reported relative to tetramethylsilane. Electrochemical investigations were carried out in an argon filled glove box using a three electrode cell with a platinum wire, platinum working and silver wire reference electrodes with the ionic liquid, 1-butyl-1-methyl-pyrrolidium NTF [BMP + -NTF ] (synthesized by Tony Burrell, Los Alamos National Lab) as the electrolyte solution. Electrochemical data were recorded using the electrochemical analyzer CHI730A-software. All UV/VIS spectra were run in 1 cm square quartz cuvettes in CH 3 Cl (unless stated otherwise). The samples were prepared and run under N 2 on a double-beam Cary-100 UV-visible spectrometer. Synthesis Yb(TMPP)Cl(DME) (14) A Schlenk flask was charged with Li 2 TmPP(DME) (1 g, 0.9 mmol) and YbCl 3 (THF) 3 (0.5 g, 0.9mmol) in a glovebox. After the addition of 40 mL of dry toluene, the flask was removed from the glovebox and the purple solution was refluxed under N 2 The progress of the reaction was monitored by UV/VIS and after 4 hours, the Soret band at 415 nm had shifted to 425 nm indicating complete metalation of the porphyrin. Toluene was removed under reduced pressure and the purple solid residue was extracted and filtered with dry CH 2 Cl 2 (2 x 30 mL). The combined extracts were reduced in volume to ca. 20 mL and layered with pentane (ca. 20mL) giving 0.8 g of purple product (64%). 1 H NMR (300 MHz, DMSO): 3.25 (w 1/2 = 2 Hz, 6 H, DME), 3.43(w 1/2 = 2Hz, 4 H, DME), 3.82 (w 1/2 = 4 Hz,12 H, -OCH3), 5.10 (w 1/2 = 2 Hz,12H,

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71 OCH3), 6.07 (w 1/2 = 5 Hz,12H, -OCH3) 7.89 (w 1/2 = 10 Hz,4H, H -ortho), 14.74 (w 1/2 = 20 Hz, 8H, H-pyrrole), 15.75 (w 1/2 = 24 Hz,4H, H -ortho). UV/VIS (CH 2 Cl 2 ) max (log ): 425 (5.27), 513 (3.77), 552 (4.34), 588 (3.81) nm. Anal. Calc. for C 60 H 62 N 4 O 14 ClYb: C, 56.69; H, 4.88; N, 4.41. Found: C, 56.58; H, 4.85; N, 4.32. Yb(TMPP)Tp (15) A solution of Yb(TmPP)Cl(DME) (0.1g 0.07 mmol) in DMF (ca. 40 mL) was stirred while potassium hydridotris(1-pyrazolyl)borate (KTp) (0.02 g, 0.07 mmol) was added. The purple solution was allowed to stir at room temperature in the glove box for 12 hours. The solvent was removed in vacuo and the purple solid was extracted with ca. 30 mL of CH 2 Cl 2 and then filtered, leaving behind a brown residue. The purple solution was reduced in volume to ca. 10 mL and then layered with ca. 20 mL of pentane. After standing overnight, 0.08 g (71% yield) of purple product was collected. 1 H NMR (300 MHz, C 6 D 6 ): 22.69 (w 1/2 = 79.41 Hz, 3H, H-Tp), 14.82 (w 1/2 =18.83 Hz, 4H, H-ortho), 14.25 (w 1/2 =15.97 Hz, 8H, H-pyrrole), 7.48 (w 1/2 =14 Hz, 4H, H-ortho), 5.21 (w 1/2 =12 Hz, 12 H, HOCH 3 ), 5.08 (w 1/2 =6 Hz, 12H, H-OCH 3 ), 4.61 (w 1/2 =12 Hz, 3H, H-Tp), 3.27 (w 1/2 =10 Hz, 12H, HOCH 3 ), -2.87(w 1/2 = 12 Hz, 3H, H-Tp). UV/VIS (CH 2 Cl 2 ) max (log ): 426 (3.11), 515 (0.22), 554 (0.39), 591 (0.20) nm. Anal. Calc. for C 65 H 62 N 10 O 12 Yb: C, 57.44; H, 4.60; N, 10.31. Found: C, 57.77; H, 4.60; N, 10.31. 4(2-ethylhexyloxy)benzaldehyde (16) 96 Ethylhexyl bromide (5.64 mL, 0.032 mol) was added dropwise to a solution of 4-hydroxybenzaldehyde (3.89 g, 0.032 mol) and potassium carbonate (6.6 g, 0.048 mol) in butanone in air. The solution was refluxed for four days after which time the brown reaction mixture was filtered through Celite and the solvent removed to give brown oil. The oil was dissolved in ether (ca. 20 mL), washed with 1M NaOH (2 x 30 mL) then H 2 0

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72 (2 x 30 mL,) and dried (Na 2 SO 4 ). Purification by column chromatography [silica, methylene chloride: petroleum ether (3:2)] gave a yellow oil in 45% yield (3.54g, 1.51mmol). 1 H NMR (300 MHz, acetone): 10.17 (s, 1H), 8.15 (d, J=3 Hz, 2H), 7.37 (d, J=1.8 Hz, 2H), 4.28 (d, J=5.4 Hz 2H), 1.8-1.59 (m, 9H), 1.25-1.16 (m, 6H). 13 C: 190.5, 164.7, 132.1, 130.5, 115.2, 71.11, 39.7, 30.8, 29.45, 29.40, 29.39, 24.15, 23.36, 14.16, 11.19. 5,10,15,20-tetrakis [4-(2-ethylhexyloxy) phenyl]-porphyrin (TPPoeh) (17) To a boiling solution of propionic acid, ethylhexyloxybenzaldehyde (2.5 g, 0.01 mol) and pyrrole (0.7 mL, 0.01 mol) were added together giving a solution that turned from yellow to dark brown. The solution was refluxed for one hour and the solvent was removed under reduced pressure, leaving a brown solid. The compound was then purified by column chromatography (silica, chloroform). The purple band was collected and was reduced in volume to ca. 10 mL and then layered with ca. 20 mL of methanol to give 17 in 5% yield (0.51 g, 0.4 mmol). 1 H NMR (300 MHz, CDCl 3 ): 8.87 (s, 8H, H-pyrrole), 8.12 (d, J=8.7 Hz, 8H, H-phenol), 7.29 (d, J=11.7 Hz 8H, H-phenol), 4.15 (d, J=5.4 Hz, 8H), 1.95 (m, 8H), 1.73-1.43 (m, 28H), 1.08 (t, J =15 Hz, 12H), 0.99 (t, J=13.8 Hz, 12H) .76 (s, 1H). UV/VIS (CHCl 3 ) max (log ): 421(5.09), 520(4.06), 556(3.93), 595(3.63), 651(3.72) nm. Anal. Calc. for C 75 H 92 N 4 O 4 : C, 80.89; H, 8.33; N, 5.03. Found: C, 79.11; H, 8.56; N, 4.73. Li 2 TPPoeh(DME) 4 (18) In a Schlenk tube, the addition of lithium hexamethyldisilazide (0.07 g, 0.46 mmol) to TPPoeh, 17, (0.27 g, 0.23 mmol) in dry DME (ca. 20 mL) gave a color change from purple to blue/green. The progress of the reaction was monitored by UV/VIS and after 3 hours, the Soret band at 421 nm had shifted to 434 nm indicating complete lithiation of

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73 the porphyrin. The solution was removed in vacuo and the product was extracted with pentane (2 x 20 mL), filtered, and cooled to C to give 6 in 83% yield (0.278g). 1 H NMR (300 MHz, C 6 D 6 ): 9.26 (s, 8H, H-pyrrole), 8.39 (d, J=8.1 Hz, 8H, H-phenol), 7.33 (d, J=8.1 Hz, 8H, H-phenol), 3.96 (d, J=5.4 Hz, 8H, H-OCH 2 ), 2.12 (s, 18H, DME), 2.04 (s, 12H, DME), 1.88-1.38 (m, 36H), 1.03-0.96 (m, 24H). UV/VIS (CH 2 Cl 2 ) max (log ): 434(4.74), 573(3.94), 618(2.79) nm. Anal. Calc. for C 91 H 130 Li 2 N 4 O 12 : C, 73.56; H, 8.82; N, 3.77. Found: C, 72.12; H, 8.28, N, 4.22. YbTPPoehCl(DME) (19) To a solution of 18 (0.1 g, 0.07 mmol) in toluene (ca. 20 mL), YbCl 3 (THF) 3 (0.06 g, 0.13 mmol) was added. Upon addition of YbCl 3 the solution turned from dark blue to red. The solution was refluxed under N 2 and the progress of the reaction was monitored by UV/VIS. After 3 hours of refluxing, the Soret band had shifted to 421 nm, indicating complete metalation of the porphyrin. The solvent was then removed in vacuo and the product extracted with pentane (2 x 20 mL). The solvent was removed, leaving purple oil in 70 % yield (0.07 g). 1 H NMR (300 MHz, C 6 D 6 ): 46.41 (w 1/2 =123 Hz, 6H, DME), 15.45 (w 1/2 =28 Hz, 8H, H-pyrrole), 14.86 (w 1/2 =30 Hz, 4H, H-phenol), 9.585 (w 1/2 =20 Hz, 4H, H-phenol), 9.24 (w 1/2 =19 Hz, 4H, H-phenol), 8.31 (w 1/2 =20 Hz, 4H, H-phenol), 4.83 (w 1/2 =10 Hz, 8H, H-OCH 2 ), 2.49-1.37 (m, 60H), -17.43 (w 1/2 =240 Hz, 4H, DME). UV/VIS (CH 2 Cl 2 ) max (log ): 421(5.27), 515(3.86), 554(4.14), 594(3.92) nm. YbTPPoeh(Tp) (20) In the glovebox, KTp (0.015 g, 0.056 mmol) was added to a stirring solution of 19 (0.07 g, 0.056 mmol) in toluene (ca. 20 mL). The purple solution was stirred overnight and then the solvent removed in vacuo. The product was extracted with pentane (2 x 10 mL) and then filtered. The pentane solution was removed, giving 20 as red oil in 58%

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74 yield (0.05 g). 1 H NMR (300 MHz, C 6 D 6 ): 22.7(w 1/2 =120 Hz, 3H. H-Tp), 15.33 (w 1/2 =60 Hz, 4H, H-phenol), 14.29 (w 1/2 =30 Hz, 8H, H-pyrrole), 9.56 (w 1/2 =45 Hz, 4H, H-phenol), 8.19 (w 1/2 =90 Hz, 8H, H-phenol), 4.91 (w 1/2 =24 Hz, 8H, H-OCH 2 ), 4.80 (w 1/2 =27 Hz, 3H, H-Tp), 2.53-1.57 (m, 60H), -2.76 (w 1/2 =45 Hz, 3H, H-Tp). UV/VIS (CH 2 Cl 2 ) max (log ): 424(4.83), 515(3.17), 555(3.77), 594(3.25) nm. Li 2 TPyP(DMF) 2 (21) In the glovebox, lithium hexamethyldisilazide (0.86 g, 5.17 mmol) was added to a solution of TpyP (0.8, 1.3 mmol) in dry DMF (ca. 30 mL), which changed colors from red to green/blue. The solution was refluxed under N 2 for 12 hours. After the reaction, the solvent was removed in vacuo and the product was washed 3 times with ca. 20 mL of hexane to remove the excess lithium hexamethyldisilazide. 1 H NMR (300 MHz, DMSO-d 6 ): 8.93 (d, J=4.8Hz, 8H, H-phenol), 8.54 (s, 8H, H-pyrrole), 8.16 (d, J=6Hz, 8H, H-phenol), 7.96 (s, 2H, DMF), 2.87(s, 6H, DMF), 2.72 (s, 6H, DMF). UV/VIS (CH 2 Cl 2 ) max (log ): 434(5.34), 535(2.19), 575(3.34), 615(3.11) nm. Anal. Calc. for C 46 H 38 N 10 O 2 Li 2 : C, 71.13; H, 4.93; N, 18.03. Found: C, 70.20; H, 4.44; N, 17.77. YbTPyPCl(DME) (22) In the glovebox, YbCl 3 (THF) 3 (0.12 g, 0.25 mmol) was added to a solution of 21 (0.15 g, 0.25 mmol) in DMF (ca. 20 mL). The solution was refluxed for 12 hours under N 2 over which time the reaction mixture went from blue/green to red in color. The DMF was removed in vacuo and the red product was washed 3 times with ca. 20 mL of DME to give 0.15g (61% yield) of product. The poor solubility of this compound made it difficult to purify completely and so it was used as is for the next reaction. 1 H NMR (300 MHz, DMSO-d 6 ): 16.29 (w 1/2 =78 Hz, 4H, H-phenol), 14.71 (w 1/2 =60 Hz, 8H, H-pyrrole), 11.71 (w 1/2 =60 Hz, 4H, H-phenol), 10.07 (w 1/2 =60 Hz, 4H, H-phenol), 8.67

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75 (w 1/2 =60 Hz, 4H, H-phenol), 3.39 (12H, DME), 3.22 (18H, DME). UV/VIS (CH 2 Cl 2 ) max (log ): 425 (5.00), 513(3.45), 555(4.00), 593(3.40) nm. Anal. Calc. for C 44 H 36 ClN 8 O 2 Yb: C, 57.61; H, 3.96; N, 12.22. Found: C, 50.80; H, 3.88; N,11.80. YbTPyP(LOEt) (23) In the glovebox, K(LOEt) (0.11 g, 0.18 mmol) was added to a solution of 22 (0.2 g, 0.18 mmol) in DMF (ca. 10 mL) and stirred for 12 hours. The solution was then removed in vacuo and the desired product was extracted with CH 2 Cl 2 (2 x. 10 mL). The CH 2 Cl 2 extractions were filtered and reduced in volume to ca. 10 mL and then layered with ca. 20 mL of pentane to give 23 as a red powder in 41% yield (0.1 g). 1 H NMR (300 MHz, C 6 D 6 ): 16.86 (w 1/2 =72 Hz, 4H, H-phenol), 15.37(w 1/2 =12 Hz, 8H, H-pyrrole), 12.03 (w 1/2 =76 Hz, 4H, H-phenol), 10.11 (w 1/2 =80 Hz, 4H, H-phenol), 8.31 (w 1/2 =36 Hz, 4H, H-phenol), 7.91 (w 1/2 =30 Hz, 6H, H-OCH 2 CH 3 ), 7.34 (w 1/2 =35 Hz, 6H, H-OCH 2 CH 3 ), 2.83 (w 1/2 =12 Hz, 18H, H-OCH 2 CH 3 ), -4.86 (w 1/2 =6 Hz, 5H, H-Cp). UV/VIS (CH 2 Cl 2 ) max (log ): 425 (5.24), 510(3.95), 555(4.07), 593(3.69) nm. Anal. Calc. for C 57 H 55 N 8 O 9 YbP 3 Co: C, 51.82; H, 4.19; N, 8.48. Found: C, 49.51; H, 3.95; N, 8.02. NdPcI(DME) (24) NdI 3 (THF) 4 (0.25g 0.31mmol) and Li 2 Pc (0.162g, 0.31mmol) were added together in 40 mLof DME. The blue solution was refluxed for 12 hours under N 2 The solution was cooled to room temperature at which time the solvent was removed via canula filtration. 0.126 g (0.143 mmol, 47%) of product was isolated after filtering and drying on the Schlenk line. The complex is insoluble in all organic solvents, preventing full characterization of this material. It was used as is for the next reaction.

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76 PrPcI(DME) (25) The same procedure for 24 was used in this synthesis. To PrI 3 (THF) 4 (1.00 g, 1.2 mmol), and Li 2 PC (0.65 g, 1.2 mmol), 50 mL of DME was added and refluxed for 12 hours to give 0.695 g (0.8 mmol, 65%) of 25. NdPc(LOEt) (26) NdPcI(DME) (0.160 g, 0.18 mmol) and the K(LOEt) (0.09 g, 0.18 mmol) were stirred together in 30 mL of dry THF. After 12 hours, the blue solution was removed in vacuo and the solid was extracted with about 30 mL CH 2 Cl 2 leaving behind a white residue of KI. The volume of the CH 2 Cl 2 solution was reduced to 15 mL and then layered with pentane and allowed to sit at room temperature until the product crystallized. After 48 hours, the blue product was isolated in 65% yield (0.142 g, 0.119 mmol) via cannula filteration. 1 H NMR (C 6 D 6 ): 11.51 (w 1/2 = 5.15 Hz, 5H, H-Cp), 6.35 (w 1/2 = 13.36 Hz, 8H, H-Pc), 6.30 (w 1/2 = 12.64 Hz, 8H, H-Pc), -0.69 (w 1/2 = 31.27 Hz, 6H, OCH 2 CH 3 ), -0.98 (w 1/2 = 32.34 Hz, 6H, OCH 2 CH 3 ), -2.14 (w 1/2 = 12.67 Hz, 18H,-OCH 2 CH 3 ). UV/VIS (CH 3 Cl), max (log ) = 676(5.05), 644(2.85), 608(4.29), 342(3.86) nm. Anal. Calc. for C 49 H 51 O 9 N 8 P 3 CoNd: C, 49.37; H, 4.31; N, 9.40. Found: C,48.25; H,4.16; N,8.73. PrPc(LOEt) (27) PrPcI(DME) (0.2 g, 0.2 mmol) was allowed to react with K(LOEt) (0.135 g, 0.230 mmol) in dry THF (ca. 20 mL) for 12 hours under inert atmosphere. The solution was removed in vacuo and the complex was extracted with ca. 30 mL of CH 2 Cl 2 The volume of the blue solution was reduced to ca. 10 mL and layered with pentane (ca. 20 mL), causing the compound to precipitate. The product was isolated in 71.3% yield (0.195 g, 0.16 mmol). 1 H NMR (C 6 D 6 ): 17.48(w 1/2 = 5.61 Hz, 5H, H-Cp), 5.10(w 1/2 = 11.65 Hz,

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77 8H, H-Pc), 4.04(w 1/2 = 11.60 Hz, 8H, H-Pc), -3.27(w 1/2 = 46.90 Hz, 12H, OCH 2 CH 3 ), -4.08(w 1/2 = 13.18 Hz, 18H, OCH 2 CH 3 ). UV/VIS (CH 3 Cl), max (log ) = 674(4.97), 644(4.19), 610(4.23), 340(4.58) nm. Anal. Calc. for C 49 H 51 O 9 N 8 P 3 CoPr: C, 49.51; H, 4.32; N, 9.43. Found: C, 50.42; H, 4.22; N, 8.95. HoPc(LOEt) (28) To a dark blue solution of HoPcCl(DME) (0.125 g,0.155 mmol) in 30 mL of THF, was added K(LOEt) (0.08 g,0.15 mmol). After stirring at room temperature for 12 hours, the solution was removed in vacuo and the product was extracted with CH 2 Cl 2 (3 x 10 mL). The extracts were combined and the volume of the solution was reduced to ca. 10 mL and then layered with pentane. The blue crystals were collected in 38% yield (0.08 g, 0.065 mmol) after 12 hours. 1 H NMR (C 6 D 6 ): 53.54(w 1/2 = 64.22 Hz, 5H, H-Cp), -4.85(w 1/2 = 17.62 Hz, 8H, H-Pc), -15.17(w 1/2 = 51.41 Hz, 8H, H-Pc), -16.98(w 1/2 = 64.4 Hz, 18H, OCH 2 CH 3 ), -24.02(w 1/2 = 15.63 Hz, 6H, OCH 2 CH 3 ), -26.01 (w 1/2 = 16.69 Hz, 6H, OCH 2 CH 3 ). UV/VIS (CH 3 Cl), max (log ) 672(5.72), 642(4.41), 606(5.00), 340(5.20) nm. Anal. Calc. for C 49 H 51 O 9 N 8 P 3 CoHo: C, 48.53; H, 4.24; N, 9.24. Found: C, 47.52; H, 4.17; N, 8.0. TmPc(LOEt) (29) Using the same procedure as 28, TmPcCl(DME) (0.148 g, 0.206 mmol) and K(Klaui) (0.097 g, 0.206 mmol) were stirred together in THF to give 0.05 g (0.041 mmol, 20% yield). 1 H NMR (C 6 D 6 ): 48.62(w 1/2 = 62.53 Hz, 6H, OCH 2 CH 3 ), 47.86(w 1/2 = 19.41 Hz, 8H, H-Pc), 47.56(w 1/2 = 83.07 Hz, 6H, OCH 2 CH 3 ), 27.62(w 1/2 = 18.41 Hz, 18H, OCH 2 CH 3 ), 27.02(w 1/2 = 10.22 Hz, 8H, H-Pc), -71.83(w 1/2 = 16.69 Hz, 5H, H-Cp). UV/VIS (CH 3 Cl), max (log )= 675(5.08), 673(5.17), 645(4.48), 608(4.41), 338(4.65)

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78 nm. Anal. Calc. for C 49 H 51 O 9 N 8 P 3 CoTm: C, 48.37; H, 4.22; N, 9.21. Found: C,48.10; H, 4.10; N,8.79. XRAY of PrPc(LOEt) Data were collected at 173 K on a Siemens SMART PLATFORM equipped with A CCD area detector and a graphite monochromator utilizing MoK radiation ( = 0.71073 ). Cell parameters were refined using up to 8192 reflections. A full sphere of data (1850 frames) was collected using the -scan method (0.3 frame width). The first 50 frames were remeasured at the end of data collection to monitor instrument and crystal stability (maximum correction on I was < 1 %). Absorption corrections by integration were applied using the measured, indexed, crystal faces. The structure was solved by Direct Methods in SHELXTL5, and refined using full-matrix least squares. The non-H atoms were treated anisotropically, whereas the hydrogen atoms were calculated in ideal positions and were riding on their respective carbon atoms. The complex is located on a mirror plane which causes a disorder in the OP(OC 2 H 5 ) 2 ligand bridging the Pr and Co centers. The mirror passes through Pr, Co, two N atoms on opposite side the macrocycle, and atom C25 of the cp ring and bisects the bond between C27 and its mirror equivalent C27a. The mirror symmetry does not pass through any of the P atoms but between them causing them to occupy six positions belonging to two parts of the three OP(OC 2 H 5 ) 2 ligands rotated by an angle of 60 from each other. A total of 374 parameters were refined in the final cycle of refinement using 18773 reflections with I > 2(I) to yield R 1 and wR 2 of 3.46% and 5.45%, respectively. Refinement was done using F 2

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CHAPTER 4 POLYERMIZABLE LANTHANIDE-PORPHYRIN COMPLEXES Introduction Because our systems work without a conjugated polymer, devices were prepared by spin-casting YbTPP(L) as the only active layer. These devices, however had poor film quality when compared with blended devices and produced only 20% of the near-infrared intensity of devices consisting of blends of 5 mol% metal complexes with non-cojugated polymers. 97 So, blending our complexes with a polymer, conjugated or non-conjugated enhances device efficiency probably by minimizing self-quenching effects and by improving film quality. Blending polymers with metal complexes acting as emitting molecules has been shown to be a valuable technique in the development of efficient sources of light for LEDs. There are, however, some disadvantages to using this technique. The blending of a polymer and dopant usually results in phase separation and non-uniform dispersion of the dopant which can lead to lower luminescent efficiencies and device durability due to triplet-triplet annihilation and higher turn on voltages. 98 Minimizing phase separation should result in enhanced device performance. Lanthanide Polymers One way to improve film quality is to incorporate the dopant into the polymer. 99 Ling et al. coploymerized an Eu(vinylbenzoic acid) (thenoyltrifluoroacetone) (phenathroline) complex with a vinylcarbozole to obtain an Eu-containing copolymer for red LEDs (Figure 4.1). 100 79

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80 HCCH2OOEuNNOOF3CS2xHCCH2Nyn Figure 4.1: Eu(TTA) 2 (VBA)phen-NVK copolymer. The copolymer was prepared by free radical copolymerization of the two monomers, using AIBN as an intiator, with average molecular weights around 10,000 g/mol. Electroluminescent studies on the single-layered device produced red emission with a performance that compared favorably with those of other single layered devices and a completely homogeneous film. Other efforts to make Ln-copolymers include work by Zeng et al. who conducted EL studies on a Tb-containing polymer that produces green light 101 and work by Yang et al. who conducted EL studies on a Tb-Eu copolymer in which varying the ratio of Eu/Tb tunes the emission color. 102 Porphyrin Polymers In recent years, porphyrin oligomers and polymers have been studied for applications in sensing, non-linear optic materials, catalysts and artificial photosynthesis. 103 One example of a porphyrin polymer was reported by Haber and coworkers, who synthesized a porphyrin supported on a polyaniline system for studying

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81 its catalytic activity towards the co-oxidation of styrene and iso-butyraldehyde (Figure 4.2). 104 NNNNNHHHHNNNNNHHHH++++NNNNMSOOOSOOOSOOOSOOO---Figure 4.2: Structure of porphyrin supported in polyaniline. Other examples consist of the copolymerization of porphyrin monomers, incorporating the porphyrin in the backbone of the polymer or as a pendant group (Figure 4.3). 105,106 While there has been considerable research on the incorporation of lanthanides, porphyrins, and transition metalloporphyrins into polymer systems, there are no lanthanide-porphyrin polymer systems, perhaps due to the lack of convenient synthesis of suitable lanthanide porphyrin monomers. This chapter will discuss the synthesis of polymerizable lanthanide-porphyrin complexes in efforts to incorporate the complex into polymers.

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82 NNNNZnRRRRR=OOnCH2HCOONHNNNHPhPhPhn Figure 4.3: Examples of porphyrin polymers. Lanthanide-Porphyrin Polymer Complexes Lanthanide-vinylporphyrin Complexes Synthesis The vinyl porphryin, 5-(4-vinylphenyl)-10,15,20 triphenylprophyrin (TPPv) was synthesized in order to be co-polymerized into a polymer to study the effects of changes in phase segregation on device efficiency. The porphyrin was synthesized by one-pot mixed aldehyde condensation reaction between vinylbenzaldehyde, pyrrole and benzaldehyde, using BF 3 (OEt 2 ) cocatalysis (Figure 4.4). After stirring the mixture for an hour, oxidation by DDQ afforded a mixture of porphyrin isomers. The desired compound was isolated via column chromotagraphy, packing the column with silica gel and hexanes and eluding the desired porphyrin from CH 3 Cl/hexanes. No other combinations of the condensation were isolated. After recrystallization from a CH 3 Cl/methanol solution, TPPv (30) was collected in 14% yield.

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83 NNHNHNPhPhPhONH++34CH3ClBF3(OEt)2TPPv (30)HH Figure 4.4: Synthesis of TPPv. Lindsey and coworkers synthesized and isolated the vinylporphyrin metallated with zinc with similar results. 107 The same compound was recently synthesized by Pomogailo et al. via a Wittig reaction between 5-(4-formylphenyl)10,15,20triphenylporphyrin and trimethylenephosphorane. 108 This synthetic approach, however requires a multi-step process with each stage of the reaction needing column chromotagraphy and recrystallization to separate and purify the products. The reaction starts with the mixed aldehyde condensation reaction to form a monocyanoporphyrin. After addition of zinc acetate, the metallated porphyrin is reduced to the aldehyde. The zinc is then removed and the free base porphyrin aldehyde is reacted with the ylide to form the vinylporphyrin (Figure 4.5).

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84 CNNHNNNHPhPhPhHOCNHONH++34Zn(AcO)2Zn(TPP-CN)CHONNNNPhPhPhZnHClTPP-aldehydeNHNNNHPhPhPhYlide Figure 4.5: Synthesis of vinylporphyrin by Pomogailo et al. With the vinyl porphyrin synthesized and characterized, similar synthetic procedures as described in the previous chapters were carried out in order to metallate the porphyrin. Firstly, the TPPv dianion was synthesized by reacting TPPv with lithium hexamethyldisilazide in refluxing DME. In a salt metathesis reaction between the dianion Li 2 TPPv(DME) 2 (31) and YbCl 3 (THF) 3 YbTPPv(Cl)DME was synthesized. After stirring the mixture of the Li salt and YbCl 3 (THF) 3 for four hours at reflux, the UV/VIS spectrum of the reaction mixture showed an absorption at ~425 nm corresponding to metallated TPPv. The solution was then separated from KCl by hot filtration and removal of the solvent. The complex YbTPPvCl(DME) (32) was recrystallized from a mixture of CH 2 Cl 2 and pentane to obtain the purple material in 80% yield (Figure 4.6).

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85 NNNN2Li(DME)2+Toluenereflux, 4hrs.NNNNYbClOOYbTPPv(Cl)DME (32)YbCl3(THF)3 Figure 4.6: Synthesis of 32. In a second set of salt metathesis reactions, YbTPPv(Cl)DME was allowed to react with the capping ligands KTp or K(LOEt) to give YbTPPv(Tp) (33) or YbTPPv(LOEt) (34) (Figure 4.7), respectively. In a Schlenk flask, YbTPPv(CL)DME and the capping ligand were stirred at room temperature under nitrogen in DME. After stirring for twelve hours, complexes 33 and 34 were extracted with CH 2 Cl 2 and were then isolated as purple crystalline solids in high yields by recrystallization from mixtures of CH 2 Cl 2 and pentane. The purity of the bulk material was confirmed by elemental analysis. NNNNPhPhPhYbClOO+NNNNNNBHKTpDMErm temp, 12hrsNNNNPhPhPhYb+CoPPPEtOOOEtOEtOEtOEtOEtOONNNNPhPhPhYbrm temp, 12hrsDMEK(LOEt)YbTPPv(LOEt) (34)YbTPPv(Tp) (33) Figure 4.7: Synthesis of complexes 33 and 34.

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86 NMR studies The 1 H NMR spectrum of YbTPPvTP (33) is shown in figure 4.8. Similar to the lanthanide porphyrin complexes discussed in previous chapters, the peaks were assigned by using 1-D, 2-D and variable temperature NMR techniques. The 1-D spectrum shows 12 peaks, five of the peaks correspond to the protons from the phenyl rings, three of the peaks correspond to the Tp protons, three of the peaks correspond to the vinyl group and the twelfth peak corresponds to the pyrrole protons. Figure 4.8: 1 H NMR spectrum of YbTPPvTp (33) With relative integrals of three and a cross peak between K and L, as seen in the 2-D spectrum of 33 (Figure 4.9), peaks A, K, and L are assigned to the protons on the Tp ligand. Because of its proximity to the paramagnetic nucleus the relaxation time of peak A is too short to allow the appearance of the crosspeaks between A and either K or L in the NMR spectrum. Peaks B and H are assigned the ortho protons on the phenyl ring with relative integrals of 4 and cross peaks between only peaks D and F, respectively.

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87 With an additional cross peak with peak E and relative integrals of 4, peaks D and E are assigned the meta protons on the phenyl ring. The coupling of the vinyl proton peaks can been seen in the 1-D NMR spectrum, as well as cross coupling peaks between peaks G, I, and J, allowing the assignment of these peaks as the vinyl proton peaks. Figure 4.9: COSY NMR of 33 (top), expansion from 11-6 ppm (bottom).

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88 Metathesis reactions Through a metathesis reaction using the ruthenium-based second-generation Grubbs catalyst, a free base porphyrin substituted stilbene derivative was synthesized (Figure 4.10). LnRuCPhHRLnRuPhRPhRLnRuRLnRuRRLnRuRRRLnRuRRuPCy3ClClNNPhLnRu =R =NHNNNHPhPhPhCross metathesis catalytic cycle NHNNNHPhPhPhRR=NNHNHNPhPhPh Figure 4.10: Catalytic cycle for metathesis reaction between vinyl porphyrins.

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89 Compound 30 was treated with 10 mol% of the Ru catalyst in dry CH 2 Cl 2 at reflux under N 2 for 1 hour. The solution was then removed and the purple solid was washed several times with diethyl ether to remove unreacted porphyrin and catalyst. 109 The stilbene derivative was recrystallized in a solution of CH 3 Cl layered with pentane to obtain the compound in 32% yield. The 1 H NMR spectrum of compound 35 in figure 4.11 shows the disappearance of the vinyl protons of compound 30 from 5.5-7 ppm (inset) as well as the appearance of a new peak at ~8 ppm, corresponding to the vinylic proton of the compound. While there is no precedence for self metathesis reactions between two porphyrins, Dolphin et al. reported the first cross metathesis reaction between vinyl porphyrins and a variety of terminal olefins. 110 They found that high loading of the catalyst was required to ensure high yields. Typical reactions used 25 mol% catalyst and when the loading was reduced to 15 mol%, the yield would drop from 100% to 70%. For the dimeraztion reaction of 30, only 10 mol% catalyst loading was used, which perhaps accounts for the observed low yield.

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90 Figure 4.11: P1PH NMR spectrum of 35 (aromatic region of 30 in inset). The YbTPPTp (36) substituted stilbene derivative was synthesized using the ruthenium-based second-generation Grubbs catalyst in the same manner as described for the free base synthetic procedure (Figure 4.12). Compound 33 was treated with 10 mol% of the Ru catalyst in dry CH 2 Cl 2 at reflux under N 2 for 12 hours. The solution was then removed and the purple solid was washed several times with diethyl ether to remove unreacted porphyrin and catalyst. 109 The stilbene derivative was recrystallized in a solution of CH 2 Cl 2 layered with pentane to obtain the compound in 25% yield. The 1 H NMR spectrum of the phenyl region of compound 36 in figure 4.13 shows the disappearance of the vinyl protons of compound 33 (inset) as well as the appearance of a new peak at ~8.9 ppm, corresponding to the vinylic protons of the compound.

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91 NNNNNNBHNNNNPhPhPhYbNNNNNNBHNNNNPhPhYbPhYbTPPvTp10 mol% Ru-catalystreflux, CH2Cl236 Figure 4.12: Synthesis of 36. Through the relative integrals in the 1-D 1 H NMR spectrum, comparison with the spectrum of 33 and the cross peaks in the 2-D spectrum, the eleven peaks are assigned. With relative integrals of 6, peaks G, F, E and C are assigned to the phenyl protons. These assignments are confirmed by the cross peaks between G and F, F and E, E and D, and D and C (Figure 4.14) seen in the 2-D spectrum. A cross peak between peaks B and A and relative integrals of 4 allow for the assignment of these peaks to the phenyl protons of the stilbene derivative. Peak H has a relative integral of 2 and is assigned to the vinylic protons of the stilbene derivative.

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92 Figure 4.13: 1 H NMR spectrum of the phenyl region of 36 (33 in inset). Figure 4.14: 2-D NMR spectrum of the phenyl region of 36.

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93 Reaction time was increased for the self metathesis reaction of 33, however, the catalyst loading remained the same. As with the cross metathesis reaction of 30, a low yield was obtained, perhaps due to the low catalyst loading. Due to the lack of complex 33, optimization of the reaction could not be completed. Polymerization In order to incorporate the lanthanide-porphyrin complex into a polymer, YbTPPvTp was copolymerized with styrene. The copolymerization takes place via a free-radical chain growth mechanism in which the reaction follows the usual free radical initiated polymerization as shown in figure 4.15. NNCCAIBNCH3CNCH3NCH3CH3CNNCCCH3CNCH3NCH3CH3C..N2CNCH3CH3C.+1. InitiationCNCH3CH3C.+StyreneCHCH2II.2. Chain PropagationCHCH2I.R+HCCH2I.CH2CHR3. TerminationHCCH2.CH2CHRHCCH2.CH2HCR+HCCH2CH2HCRHCCH2CH2HCRnnn Figure 4.15: Scheme of a free radical chain growth mechanism.

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94 Styrene and the initiator 2,2-azobisisobutyronitrile (AIBN) were added to complex 33 with concentrations of 20, 10,and 5 mol%. The neat mixture was stirred overnight at 60 C under N 2 After 12 hours, the purple solution turned into a solid material that was completely insoluble in most organic solvents. The solid was washed several times with THF and what was soluble in THF was analyzed by GPC and found to be monomeric species. Copolymerization reactions with styrene and the free base vinylporphyrin as well as zinc and copper complexes of the porphryin were performed by Pomogailo et al. 108 who showed that even when concentrations of the vinylporphyrin were ~ 0.5 mol%, THF-insoluble polymers were formed. Studies of device construction have found that the best operating devices contained blends of lanthanide-porphyrin complex between 5 and 15 mol%. 73 In order to synthesize a soluble polymer with higher concentrations of the lanthanide-porphyrin complex, copolymerization reactions were carried out with 4-t-butylstyrene (t-BS) and 2,2,2-trifluoroethyl methacrylate (TFEM) (homopolymers containing t-BS are generally brittle and make a poor quality films) (Figure 4.16). 111 OOFFFt-BSTFEM Figure 4.16: Chemical structures of monomers.

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95 A copolymerization reaction was carried out with equimolar amounts of t-BS and TFEM, 1 mol% of 33 and 0.2 mol% of the initiator AIBN in toluene (copolymerizations that were run neat produced a completely insoluble gel). After heating at 60 C under N 2 for 20 hours, the polymer was dissolved in a small amount of CH 2 Cl 2 and precipitated by addition of methanol to give a light pink powder. The polymer is soluble in most organic solvents, including CH 2 Cl 2 CH 3 Cl, THF and hexane. The weight average molecular weight (M w ) and the number average molecular weight (M n ) of the polymer were found to be ~ 200,000 and 90,000 with a polydispersity of 2 determined by GPC analysis. The absorption spectrum of the polymer showed the Soret band ~420nm, but the Q bands were too weak to detect. Emissions from Yb 3+ were too weak to detect. First attempts at a polymerization reaction with 10 mol% did not yield any Ln-porphyrin containing polymer. Tp Polymer Polymers containing trispyrazole borate (Tp) units were synthesized by Prof. Frieder Jaekles group, at Rutgers University, in order to incorporate LnTPP complexes into polymers (Figure 4.17). HCCH2BNNNNNNHCCH2Si37Na+Figure 4.17: Structure of Tp polymer.

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96 The copolymer that contained 30% Tp and a sodium counter ion was stirred with YbTPPCl(DME) in dry DMSO at 60 degrees C (Figure 4.18). After 2 days, the solution was removed in vacuo and the copolymer was isolated. The polymer was found to be insoluble in most organic solvents, including THF, DME, and CH 2 Cl 2 The crude material was washed several times with THF and CH 2 Cl 2 to remove any impurities, unreacted YbTPPCl(DME) and the by-product, KCl. HCCH2BNNNNNNHCCH2Si37Na+-+YbTPPCl(DME)HCCH2BNNNNNNHCCH2Si37NNNNYbDMSO2 days Figure 4.18: Synthesis of YbTPP-Tp (37) polymer. Absorption studies performed in dichlorobenzene showed typical metallated porphyrin spectra with the Soret band ~ 423nm and three Q bands between 520 and 630nm (Figure 4.19). Emission studies showed Yb-emission ~980 nm emission of the Yb 3+ 2 F 5/2 2 F 7/2 transition with weaker emission bands at lower wavelengths, which is attributed to the crystal field splitting of the Yb 3+ f-states by the axial and porphyrin ligands (figure 4.20). Efforts to find a solvent that dissolves the polymer and is suitable for device construction are underway.

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97 Figure 4.19: Absorption spectrum of 37 (inset shows Q bands). Figure 4.20: NIR emission spectrum of 37. Summary An effort to incorporate a lanthanide-porphyrin complex into a polymer has led to the synthesis and characterization of new Yb-vinylporphyrin complexes. These vinylporphyrin complexes have been found to undergo a self metathesis reaction with a Ru-based Grubbs catalyst to give porphyrin and Yb-porphyrin stilbene derivatives. Attempts to copolymerize the Yb-vinylporphyrin complex with styrene produced insoluble copolymers, with loading as low as 5 mol% YbTPPvTp. Copolymerization

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98 reactions of vinylporphyrin metal complexes with styrene or methylmethacrylate carried out by Pomogailo and coworkers produced soluble copolymers when 0.5 mol% the porphyrin monomer was used. Higher concentrations of porphyrin monomer produced insoluble polymers and as the concentration of porphyrin monomer increased, the appearance of the gel effect is increased. When the concentrations of monomers are high, the viscosity of the reaction mixture becomes high as polymer chains form. Due to the high viscosity, the diffusion of polymer chains becomes hindered and the rate of termination is decreased. Small monomers, however, can still diffuse and chains grow without terminations, producing polymers with extremely high molecular weights. Copolymerizations of YbTPPvTP and styrene were carried out neat and so concentrations of the monomers were high and perhaps producing polymers with too high of a molecular weight. Future work in the copolymerization of the lanthanide porphyrin complexes with styrene should be carried out in solution in efforts to curb the gel effect. Copolymerization reactions of tBS, TFEM and YbTPPvTp were run in an effort to produce a more soluble copolymer. In toluene solution, 1 mol% of YbTPPvTp, tBS, TFEM and the initiator AIBN were reacted to give a soluble polymer with high molecular weight. So, changing from styrene to a more soluble tBS as well as running the polymerization reaction in solution afforded soluble Yb-porphyrin containing polymers. The Yb-porphyrin content in the polymer, however, was too small to detect Yb emission. The first attempt at increasing YbTPPvTP concentration in the polymer was carried out in a more dilute solution and yielded no polymers. Future work should optimize the polymerization conditions, focusing on the dilution of the solution.

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99 The synthesis of Tp-polymers provide another means to incorporate LnTPP complexes into polymers. A salt metathesis reaction between YbTPPCl(DME) and NaTp-polymer yielded the Yb-TPP incorporated polymer. Absorption and NIR emission studies show typical LnTPP absorption and Yb-emission. The copolymer was not soluble enough in any solvents to make devices. Incorporation of a more soluble lanthanide-porphyrin complex such as Yb(TPPeoh)Cl would perhaps increase the solubility of the polymer. Experimental Materials and Reagents Unless otherwise stated, all syntheses were carried out on a double manifold Schlenk line under an atmosphere of nitrogen or in a N 2 filled glovebox. Glassware was oven dried prior to use. Methylene chloride, dimethoxyethane, chloroform, DMSO and dimethlyforamide were purchased from Fisher Scientific and were dried with an appropriate drying agent. 77 Pentane, tetrahydrofuran and toluene were purchased from Aldrich Chemicals and dried by passing through a column of activated alumina. Following dehydration, all solvents were degassed and stored over 4 molecular sieves in resealable ampoules with fitted Teflon valves. Anhydrous dichlorobenzene was purchased from Aldrich and used as it was received. The monomers styrene and t-BS were purchased from Aldrich. TFEM was purchased from SynQuest Labs in Alachua, FL. All monomers were run through basic alumina prior to use. The initiator AIBN was purchased from Aldrich and recrystallized from methanol prior to use. The complexes (Cyclopentadienyl)tris(diethylphospinito)cobalt (LOEt), 78 hydridotris(1-pyrazolyl)borate (Tp H ), 79 and YbTPPCl(DME) 51 were synthesized following literature procedures. The Tp-polymer was provided by Professor Frieder Jaekle at Rutgers University. The

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100 second-generation Grubbs catalyst was provided by Professor Ken Wagener at the University of Florida. Elemental analyses were performed at the University of California, Berkley, Micro-Mass Facility or University of Florida Spectroscopic Services. Proton NMR spectra were measured at 300 MHz at room temperature unless otherwise stated on Varian, Gemini 300, VXR 300, Mercury 300 or Bruker 300 NMR machines. Chemical shifts were referenced to residual solvent peaks and are reported relative tetramethylsilane. The spectral window was also different for each metal complex and was determined by expanding the window until peak positions remained unchanged. COSY spectra were run using the standard parameters of the instrument. All UV/VIS spectra were run in 1 cm path length quartz cuvettes in CH 3 Cl unless stated otherwise. The samples were prepared and run under N 2 on a double-beam Cary-100 UV-visible spectrometer. GPC analysis was run in THF on a Dynamax GPC with the Spectroflow 757 absorbance detector set at 420 nm and calibrated to polystyrene standards. Synthesis TPPv (30) Following the procedure for mixed aldehyde condensation, 107, 112 (diethylacetal)vinylphenyl (2 g, 10 mmol), pyrrole (2.8 mL, 40 mmol) and benzaldehyde (3.16 mL, 30 mmol) were condensed in ca. 700 mL of CHCl 3 in the presence of BF 3 (OEt) 2 (0.78 mL, 6.7 mmol) at room temperature. After 1 hour, DDQ (6 g, 30 mmol) was added and solution was stirred for 5 minutes. `The solution was filtered and run through a silica column (packed with hexanes) with CH 3 Cl/hexanes (3:1) as the eluant. The first purple band was collected and the solvent was removed. Recrystallization from CH 2 Cl 2 / methanol (10 mL/ 30 mL) gave 0.9 g (1.4 mmol, 14% yield) of product. 1 H NMR (300 MHz, CDCl 3 ): 8.89 (m, 8H), 8.27 (m, 8H), 7.79 (m, 12H), 7.11 (dd,

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101 J1=10.98 Hz, J2=10.98, 1H), 6.11 (d, J=17.7 Hz, 1H), 5.52 (d, J=10.99 Hz, 1H), .38 (s, 2H). UV/VIS (CH 2 Cl 2 ) max (log ): 422(4.55), 518(3.28), 552(2.98), 595(2.95), 662(3.18) nm. Anal. Calc. for C 46 H 30 N 4 : C, 86.52; H, 4.70; N, 8.78. Found: C, 85.28; H, 4.99; N, 8.37. Li 2 TPPv(DME) 2 (31) In a Schlenk flask, TPPv (0.1 g, 0.016 mmol) was added to lithium hexamethyldisilazane (0.05 g, 0.032 mmol) in ca. 10 mL of dry DME. The solution was refluxed under nitrogen for 12 hours, after which the color changed from red to green/blue and the product precipitated. The solution was filtered, leaving behind the product in 75% yield (0.1 g, 0.012 mmol). 1 H NMR (300 MHz, C 6 D 6 ): 9.05 (m, 8H), 8.30 (m, 8H), 7.54 (m, 12H), 6.95 (dd, J 1 = 10.47 Hz, J 2 = 10.47, 1H), 5.94 (d, J= 17.57 Hz, 1H), 5.32 (d, J= 10.74, 1H), 1.63 (DME, 20H). UV/VIS (CH 2 Cl 2 ) max (log ): 435(5.56), 554(4.43), 603(4.44) nm. YbTPPvCl(DME) (32) In a Schlenk flask, Li 2 TPPv(DME) 2 ( 0.1 g, 0.12 mmol) and Yb(Cl) 3 (0.033 g, 0.12 mmol) were added together in ca. 20 mL of toluene. The solution was refluxed under N 2 for 3 hours, during which the green/blue solution turned red. The compound was isolated by filtration and removal of the solution. Recrystallization from CH 2 Cl 2 (10 mL) layered with hexane (30 mL) gave 0.09 g (80% yield, 0.096 mmol) of product. 1 H NMR (300 MHz, CDCl 3 ): 44.23 (w 1/2 = 5.47 Hz, 4H, DME), 15.81 (w 1/2 = 10 Hz, 5H, H-phenyl), 14.68 (w 1/2 = 23 Hz, 8H, H-pyrrole), 10.27 (w 1/2 = 21 Hz, 5H, H-phenyl), 9.34 (w 1/2 = 17 Hz, 9H, H-phenyl), 8.25 (dd, J 1 = 10.9 Hz, J 2 = 10.9, 1H), 7.09(d, J= 18 Hz, 1H), 6.30 (d, J= 11 Hz, 1H), -19.74(w 1/2 = 3 Hz, 6H, DME). UV/VIS (CH 2 Cl 2 ) max (log ): 422(4.07),

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102 512(2.64), 551(2.97), 590 (2.64) nm. Anal. Calc. for C 50 H 40 N 4 O 2 ClYb: C, 64.10; H, 4.27; N, 5.98. Found: C, 64.32; H, 4.27; N, 5.56. YbTPPv(Tp) (33) In DME (ca. 10 mL), YbTPPvCl(DME) ( 0.35 g, 0.38 mmol) and KTp (0.094 g, 0.35 mmol) were added together and stirred overnight at room temperature. The solvent was then removed in vacuo and the product was extracted with ca. 20 mL of CH 2 Cl 2 The CH 2 Cl 2 solution was reduced in volume to ca. 5 mL and then layered with pentane (ca. 10 mL). After being cooled to 0 C for 12 hours, the solution was filtered, leaving a purple solid. The mother liquor was reduced in volume (ca.10 mL) to allow more product to precipitate. The combined solids were collected giving a yield of 69% (0.25 g, 0.24 mmol). 1 H NMR (300 MHz, CDCl 3 ): 22.5(w 1/2 = 16 Hz, 3H, H-Tp), 15.60(w 1/2 = 4 Hz, 4H, o-C 6 H 5 Tpp), 13.81(w 1/2 = 16 Hz, 8H, H-pyrrole), 10.11(w 1/2 = 29 Hz, 4H, m-C 6 H 5 Tpp), 9.13(w 1/2 = 5 Hz, 4H, p-C 6 H 5 Tpp), 8.44(w 1/2 = 30 Hz, 4H, m-C 6 H 5 Tpp), 8.07(dd, J 1 = 11 Hz, J 2 = 11 Hz 1H, H-vinyl) 7.86(w 1/2 = 15 Hz, 4H, o-C 6 H 5 Tpp), 7.01(d, J=17 Hz, 1H, H-vinyl), 6.18(d, J=11 Hz, 1H, H-vinyl), 4.89(w 1/2 = 8 Hz, 3H, H-Tp), -2.68(w 1/2 = 15 Hz, 3H, H-Tp). UV/VIS (CH 2 Cl 2 ) max (log ): 423(5.07), 513(3.56), 552(3.92), 589(3.55) nm. Anal. Calc. for C 55 H 40 N 10 BYb: C, 64.46; H, 3.91; N, 13.61. Found: C, 64.25; H,3.88; N,13.53. YbTPPv(LOEt) (34) Using a procedure similar to that used for the preparation of 33, 34 was synthesized by stirring YbTPPvCl(DME) (0.2 g, 0.2 mmol) and K(LOEt) (0.1 g, 0.2 mmol) together in DME (ca. 10 mL) at room temperature. After 12 hours of stirring, the purple solution was removed in vacuo and the product was extracted with ca. 20 mL of CH 2 Cl 2 leaving behind a residue of KCl. The CH 2 Cl 2 solution was reduced in volume (ca. 5 mL) and

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103 layered with pentane (10 mL) to precipitate the product in 60% yield (0.16 g, 0.12 mm0l). 1 H NMR (300 MHz, C 6 D 6 10 degrees C): 17.14 (w 1/2 = 22 Hz, 4H, o-C 6 H 5 Tpp), 15.56 (w 1/2 = 8 Hz, 8H, H-pyrrole), 10.48 (w 1/2 = 20 Hz, 4H, m-C 6 H 5 Tpp), 9,18(w 1/2 = 4 Hz, 3H, p-C 6 H 5 Tpp), 8.74(w 1/2 = 13 Hz, 4H, m-C 6 H 5 Tpp), 8.53(w 1/2 = 22 Hz, 4H, o-C 6 H 5 Tpp), 8.19(w 1/2 = 29 Hz, 6H, OCH 2 CH 3 ) 8.07 (w 1/2 = 6 Hz 1H, H-vinyl) 7.39(w 1/2 = 3 Hz, 6H, OCH 2 CH 3 ), 7.01(d, J=17 Hz, 1H, H-vinyl), 6.14(d, J=11 Hz, 1H, H-vinyl), 2.85(w 1/2 = 10 Hz, 18H, OCH 2 CH 3 ), -4.83(w 1/2 = 4 Hz, 5H, H-Cp). UV/VIS (CH 2 Cl 2 ) max (log ): 425(4.58), 514(3.12), 557(3.46), 596(3.12) nm. TPP-TPP (35) In a Sclenk flask, TPPv (0.168g, 0.26mmol) and 10 mol % of second-generation Grubbs catalyst were added together in ca. 3 mL of CH 2 Cl 2 The flask was fitted with a reflux condenser and the solution was stirred at reflux under nitrogen for one hour. The solution was removed in vacuo and the product was washed with diethyl ether (3 x 10 mL). The product was recrystallized from CH 2 Cl 2 layered with pentane to give the stilbene derivative in 32% yield (0.1 g, 0.07 mmol). 1 H NMR (300 MHz, CDCl 3 ): 8.99(m, 16H), 8.22(m, 16H), 8.08(d, 2H), 7.79(m, 24H), -2.69(s, 2H), -2.75(s, 2H). UV/VIS (CH 2 Cl 2 ) max (log ): 416(5.30), 514(4.25), 550(4.01), 588(3.84), 644(3.81) nm. Anal. Calc. for C 90 H 60 N 8 : C, 86.24; H, 4.82; N, 8.94. Found: C, 82.47; H, 4.78; N, 8.18. YbTPPTp-YbTPPTp (36) In a Sclenk flask, YbTPPvTp (0.02g, 0. 02mmol) and 10 mol % of second-generation Grubbs catalyst were added together in ca. 3 mL of CH 2 Cl 2 The flask was fitted with a reflux condenser and the solution was stirred at reflux under nitrogen for 12 hours. The solution was removed in vacuo and the product was washed with diethyl

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104 ether (3 x 10 mL). The product was recrystallized from CH 2 Cl 2 layered with pentane to give 36 in 24% yield (0.01 g, 0.005 mmol). 1 H NMR (300 MHz, CDCl 3 ): 22.6(w 1/2 = 8 Hz, 6H, H-Tp), 15.5(w 1/2 = 24 Hz, 6H, o-C 6 H 5 Tpp), 13.81(w 1/2 = 16 Hz, 16H, H-pyrrole), 10.11(w 1/2 = 30 Hz, 6H, m-C 6 H 5 Tpp), 9.13(w 1/2 = 5 Hz, 6H, p-C 6 H 5 Tpp), 8.86(w 1/2 = 15 Hz, 4H, H-vinyl), 8.42(w 1/2 = 30 Hz, 6H, m-C 6 H 5 Tpp), 8.20(w 1/2 = 15, 4H, H-stilbene derivative), 7.78(w 1/2 = 15 Hz, 10H, o-C 6 H 5 Tpp, H-stilbene), 4.89(w 1/2 = 8 Hz, 6H, H-Tp), -2.84(w 1/2 = 15 Hz, 6H, H-Tp). UV/VIS (CH 2 Cl 2 ) max (log ): 421(5.32), 513(3.88), 550(4.31), 590(3.88) nm. YbTPP-Tp polymer (37) In a Schlenk flask in the glove box, YbTPPCl(DME) (0.06 g, 0.07mmol) was added to a solution of the 30% NaTp-polymer (0.07 g) in d 6 -DMSO (10 mL). The solution was stirred at room temperature for 12 hours. 1 H NMR revealed no change to the polymer spectrum. The solution was heated to 60 degrees C for 12 hours. The solution was then removed in vacuo and a pink and white solid were present in the flask. The crude material was washed with CH 2 Cl 2 DME and THF, leaving behind the pink product, which is insoluble in most organic solvents. UV/VIS and emission studies were carried out in dichlorobenzene. Copolymerizations All polymerizations were performed in a Schlenk flask stoppered with a septum under an atmosphere of N 2 YbTPPvTp (0.04 g, 0.03 mmol, 1 mol%) was introduced to the flask and the monomers, t-BS (0.35 mL, 1.9 mmol) and TFEM (0.27mL, 1.9 mmol) were dissolved in toluene (2 x monomer volume) and added to the YbTPPvTp complex. The initiator, AIBN (0.0012g, 0.0076 mmol, 0.2 mol% of AIBN relative to the total mass of monomers) was then added to the stirring toluene solution of YbTPPvTP and the

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105 monomers. The solution was heated to 60 degrees C for 48 hours. The solution was removed and CH 2 Cl 2 (1 mL) was added to the crude material. Methanol was added to the solution until the polymer precipitated. GPC analysis (in THF, polystyrene standards): M w : 200,000, M n : 90,000 with a polydispersity of 2.

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CHAPTER 5 CONCLUSIONS In conclsuion, novel lanthanide-porphyrin complexes have been synthesized and characterized for emitting materials in NIR LEDs. Through a simple salt metathesis reaction with the corresponding lanthanide trihalides and dilithio-porphyrin complexes, LnPorphyrin(X)(DME) complexes were cleanly isolated in good yields. From this starting material, the lanthanide compounds were easily complexed with a number of ancillary ligands including Tp, LOEt and quinolate. Through these synthetic procedures, lanthanide-porphyrin complexes with a variety of capping ligands and porphyrin-phenyl ring substituents were easily synthesized and isolated in yields ranging from 30% to 75%. These compounds have been fully characterized through crystallographic methods, proton and COSY NMR studies, UV/Vis spectroscopy and elemental analysis. PL studies of the complexes found that NdTPP(Tp) and NdTPP(LOEt) complexes produced NIR emission around 900 nm, 1069 nm and 1300 nm with quantum efficiencies around 2.4%. The Yb(porphyrin)L complexes produced NIR emission around ~980 and ~1020 nm with quantum efficiencies as high as 4.1%. Emission spectra are easily tuned by changing the lanthanide ion in the porphyrin complex. There is little change, however, in PL efficiency when the capping ligands or porphyrin-phenyl ring substituents are varied. These lanthanide-porphyrin complexes have higher NIR quantum yields than other reported lanthanide complexes, perhaps due to the effective sensitization of the porphyrin chromophore and the effective shielding of the capping ligand. New LnPc monomeric complexes were synthesized and fully characterized, but produced no NIR 106

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107 emission because the triplet state of Pc (1050 nm) is too low in energy to sensitize Nd-, Pr-, Ho-, Tmand YbPc(LOEt) complexes. When the capping ligand is not sterically encumbering enough to hinder solvent coordination, in the instance of YbTPPQ(THF), the solvent molecule facilitates nonradiative decay and lowers quantum efficiency. Future efforts to improve PL quantum efficiency should perhaps focus on designing Ln(porphyrin)L complexes with fewer C-H and O-H molecules in close proximity to the lanthanide ion. EL studies carried out with blends of Ln(porphyrin)L and PS show that these complexes act as the charge carrier as well as the emitting species. Devices produced NIR emission with external quantum efficiencies around ~1 x 10 -4 (with exception to YbTPPQTHF which was 2 x 10 -5 ). There is no change in emission or device efficiency when the capping ligands or porphyrin-phenyl ring substituents are varied, perhaps because the factors involved in device construction outweigh any differences that arise from the identity of the porphyrin substituents. Studies on devices blended with AlQ 3 produce NIR emission with quantum efficiencies ten times higher than devices without AlQ 3 suggesting that LnTPP(L) is more efficient in the transport of holes than electrons therefore, creating a charge imbalance and lowering of device efficiencies. Improvement of device efficiencies could then perhaps be obtained by incorporating an electron transport layer. An effort to incorporate a lanthanide-porphyrin complex into a polymer has led to the synthesis and characterization of new Yb-vinylporphyrin complexes. Attempts to copolymerize the Yb-vinylporphyrin complex with styrene produced insoluble copolymers, with loading as low as 5 mol% YbTPPvTp. Copolymerization reactions of

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108 vinylporphyrin metal complexes with styrene or methylmethacrylate carried out by Pomogailo and coworkers produced soluble copolymers when 0.5 mol% the porphyrin monomer was used. Higher concentrations of porphyrin monomer produced insoluble polymers and as the concentration of porphyrin monomer increased, the appearance of the gel effect is increased. When the concentrations of monomers are high, the viscosity of the reaction mixture becomes high as polymer chains form. Due to the high viscosity, the diffusion of polymer chains becomes hindered and the rate of termination is decreased. Small monomers, however, can still diffuse and chains grow without terminations, producing polymers with extremely high molecular weights. Copolymerizations of YbTPPvTP and styrene were carried out neat and so concentrations of the monomers were high and perhaps producing polymers with too high of a molecular weight. Future work in the copolymerization of the lanthanide porphyrin complexes with styrene should be carried out in solution in efforts to curb the gel effect. Copolymerization reactions of tBS, TFEM and YbTPPvTp were run in an effort to produce a more soluble copolymer. In toluene solution, 1mol% of YbTPPvTp, tBS, TFEM and the initiator AIBN were reacted to give a soluble polymer with M w and M n around ~ 200,000 and 90,000, respectively. The Yb-porphyrin content in the polymer, however, was too small to detect Yb emission. The first attempt at increasing YbTPPvTP concentration in the polymer was carried out in a more dilute solution and yielded no polymers. Future work should optimize the polymerization conditions, focusing on the dilution of the solution. The synthesis of Tp-polymers provide another means to incorporate LnTPP complexes into polymers. Absorption studies performed in dichlorobenzene showed

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109 typical metallated porphyrin spectra with the Soret band ~ 423nm and three Q bands between 520 and 630nm and NIR emission studies showed Yb-emission at ~980 nm emission. The copolymer was not soluble enough in any solvents to make devices. Incorporation of a more soluble lanthanide-porphyrin complex such as Yb(TPPeoh)Cl would perhaps increase the solubility of the polymer.

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APPENDIX CRYSTALLOGRAPHIC INFORMATION Information for the crystal structure of 3 Table 1. Crystal data and structure refinement for 3. Identification code ak02 Empirical formula C56 H52 I N4 Nd O3 Formula weight 1100.16 Temperature 173(2) K Wavelength 0.71073 Crystal system Triclinic Space group P-1 Unit cell dimensions a = 12.4470(11) = 69.585(2). b = 14.5765(13) = 74.880(2). c = 14.6837(13) = 89.225(2). Volume 2401.5(4) 3 Z 2 Density (calculated) 1.521 Mg/m3 Absorption coefficient 1.772 mm-1 F(000) 1106 Crystal size 0.24 x 0.08 x 0.05 mm3 Theta range for data collection 1.54 to 27.50. Index ranges -16h15, -18k18, -18l19 Reflections collected 21110 Independent reflections 10631 [R(int) = 0.0462] Completeness to theta = 27.50 96.5 % Absorption correction Integration Max. and min. transmission 0.9243 and 0.7470 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 10631 / 0 / 548 Goodness-of-fit on F2 0.964 110

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111 Final R indices [I>2sigma(I)] R1 = 0.0406, wR2 = 0.1031 [7861] R indices (all data) R1 = 0.0562, wR2 = 0.1075 Extinction coefficient 0.0061(4) Largest diff. peak and hole 1.162 and -0.790 e.-3 R1 = (||Fo| |Fc||) / |Fo| wR2 = [[w(Fo2 Fc2)2] / [wFo22]]1/2 S = [[w(Fo2 Fc2)2] / (n-p)]1/2 w= 1/[2(Fo2)+(m*p) 2 +n*p], p = [max(Fo2,0)+ 2* Fc2]/3, m & n are constants. Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (2x 103) for 3 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________ x y z U(eq) ________________________________________________________________________ Nd1 6901(1) 2213(1) 714(1) 19(1) I1 5044(1) 492(1) 2158(1) 40(1) I2 5127(11) 3785(10) 222(10) 99(4) O1 5556(3) 2458(3) -392(2) 34(1) O2 5553(3) 3180(2) 1583(2) 34(1) N1 7881(3) 2447(2) 1869(3) 21(1) N2 8030(3) 841(2) 1069(3) 19(1) N3 8047(3) 2222(2) -913(3) 19(1) N4 7936(3) 3838(2) -134(2) 20(1) C1 8078(4) 3309(3) 2011(3) 22(1) C2 8370(4) 3076(3) 2955(3) 26(1) C3 8349(4) 2100(3) 3362(3) 28(1) C4 8062(3) 1691(3) 2679(3) 22(1) C5 8063(3) 694(3) 2800(3) 21(1) C6 8045(3) 306(3) 2048(3) 20(1) C7 8074(4) -715(3) 2185(3) 24(1) C8 8109(4) -800(3) 1285(3) 26(1) C9 8105(3) 185(3) 578(3) 22(1) C10 8258(3) 439(3) -470(3) 21(1) C11 8310(3) 1411(3) -1161(3) 21(1)

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112 C12 8663(4) 1694(3) -2251(3) 27(1) C13 8624(4) 2681(3) -2638(3) 29(1) C14 8233(3) 3019(3) -1810(3) 22(1) C15 8159(3) 4005(3) -1908(3) 23(1) C16 8012(4) 4377(3) -1126(3) 23(1) C17 8028(4) 5411(3) -1266(3) 28(1) C18 8003(4) 5488(3) -384(3) 29(1) C19 7975(4) 4505(3) 340(3) 23(1) C20 8060(4) 4269(3) 1330(3) 23(1) C21 8197(4) 5085(3) 1688(3) 25(1) C22 9112(4) 5796(3) 1171(3) 29(1) C23 9246(5) 6575(3) 1498(4) 36(1) C24 8476(5) 6633(4) 2341(4) 41(1) C25 7572(5) 5935(4) 2862(4) 41(1) C26 7438(4) 5158(3) 2527(4) 31(1) C27 8235(4) -5(3) 3757(3) 25(1) C28 7394(5) -290(4) 4639(4) 43(1) C29 7581(6) -948(5) 5536(4) 59(2) C30 8601(6) -1307(4) 5533(4) 53(2) C31 9460(6) -1016(4) 4659(4) 54(2) C32 9261(5) -370(4) 3778(4) 38(1) C33 8429(3) -365(3) -895(3) 22(1) C34 9265(3) -1003(3) -720(3) 24(1) C35 9408(4) -1747(3) -1097(3) 29(1) C36 8747(4) -1876(3) -1674(4) 34(1) C37 7914(4) -1240(4) -1861(4) 34(1) C38 7753(4) -501(3) -1468(3) 29(1) C39 8396(4) 4742(3) -2966(3) 25(1) C40 7636(4) 4820(4) -3540(4) 35(1) C41 7874(5) 5517(4) -4520(4) 47(2) C42 8844(5) 6111(4) -4933(4) 48(1) C43 9600(6) 6015(4) -4391(4) 53(2) C44 9375(5) 5336(4) -3405(4) 40(1) C45 5580(5) 1812(5) -964(5) 55(2) C46 4419(6) 1646(7) -973(7) 86(3) C47 3862(5) 2523(5) -855(5) 58(2)

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113 C48 4438(4) 2795(4) -188(4) 39(1) C49 5132(5) 4114(4) 1135(4) 42(1) C50 4795(5) 4541(4) 1944(4) 50(2) C51 4386(5) 3643(5) 2894(5) 57(2) C52 5181(5) 2898(4) 2685(4) 42(1) Information for the crystal structure of 7 Table 1. Crystal data and structure refinement for sk01. Identification code sk01 Empirical formula C108.50 H82 B2 N20 Nd2 Formula weight 1976.04 Temperature 193(2) K Wavelength 0.71073 Crystal system Triclinic Space group P-1 Unit cell dimensions a = 12.6145(5) = 84.067(2). b = 13.7314(6) = 78.022(2). c = 27.843(2) = 74.461(2). Volume 4539.5(3) 3 Z 2 Density (calculated) 1.446 Mg/m3 Absorption coefficient 1.194 mm-1 F(000) 2006 Crystal size 0.17 x 0.05 x 0.05 mm3 Theta range for data collection 1.71 to 27.50. Index ranges -16h16, -17k17, -36l35 Reflections collected 40834 Independent reflections 20287 [R(int) = 0.0548] Completeness to theta = 27.50 97.2 % Absorption correction Analuy Max. and min. transmission 0.9471 and 0.8203 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 20287 / 0 / 1208 Goodness-of-fit on F2 0.840 Final R indices [I>2sigma(I)] R1 = 0.0369, wR2 = 0.0642 [12451]

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114 R indices (all data) R1 = 0.0756, wR2 = 0.0697 Extinction coefficient 0.00003(3) Largest diff. peak and hole 0.584 and -0.836 e.-3 R1 = (||Fo| |Fc||) / |Fo| wR2 = [[w(Fo2 Fc2)2] / [wFo22]]1/2 S = [[w(Fo2 Fc2)2] / (n-p)]1/2 w= 1/[2(Fo2)+(0.0176*p) 2 +0.00*p], p = [max(Fo2,0)+ 2* Fc2]/3 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (2x 103) for 7. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________ x y z U(eq) ________________________________________________________________________ Nd 5271(1) 7773(1) 8574(1) 20(1) B 4016(4) 8029(3) 7456(2) 31(1) N1 7263(2) 7536(2) 8574(1) 22(1) N2 5873(2) 6127(2) 8983(1) 22(1) N3 4071(2) 7789(2) 9376(1) 20(1) N4 5440(2) 9210(2) 8986(1) 21(1) N5 5444(3) 6661(2) 7850(1) 34(1) N6 4773(2) 6958(2) 7505(1) 30(1) N7 3268(2) 8125(2) 8375(1) 30(1) N8 3065(2) 8235(2) 7911(1) 28(1) N9 5248(2) 8939(2) 7774(1) 27(1) N10 4716(2) 8820(2) 7408(1) 26(1) C1 7804(3) 8303(3) 8468(1) 23(1) C2 8995(3) 7854(3) 8335(1) 29(1) C3 9162(3) 6844(3) 8391(1) 29(1) C4 8077(3) 6637(3) 8536(1) 23(1) C5 7904(3) 5660(3) 8647(1) 23(1) C6 6868(3) 5429(3) 8836(1) 23(1) C7 6696(3) 4421(3) 8908(1) 29(1) C8 5597(3) 4514(3) 9092(1) 29(1)

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115 C9 5090(3) 5580(2) 9160(1) 22(1) C10 4008(3) 5998(3) 9417(1) 22(1) C11 3597(3) 7002(2) 9562(1) 20(1) C12 2642(3) 7353(3) 9936(1) 26(1) C13 2529(3) 8347(3) 9974(1) 27(1) C14 3424(3) 8628(3) 9615(1) 23(1) C15 3576(3) 9620(3) 9534(1) 21(1) C16 4530(3) 9876(3) 9246(1) 23(1) C17 4734(3) 10870(3) 9200(1) 25(1) C18 5768(3) 10789(3) 8919(1) 27(1) C19 6227(3) 9751(3) 8793(1) 22(1) C20 7319(3) 9336(3) 8539(1) 22(1) C21 8917(3) 4784(3) 8591(1) 26(1) C22 9572(3) 4539(3) 8136(2) 42(1) C23 10500(4) 3739(4) 8091(2) 63(2) C24 10787(4) 3185(3) 8500(2) 62(2) C25 10168(4) 3410(3) 8956(2) 52(1) C26 9228(3) 4221(3) 9005(2) 36(1) C27 3211(3) 5328(3) 9575(1) 24(1) C28 3454(3) 4469(3) 9881(1) 31(1) C29 2708(3) 3875(3) 10020(1) 39(1) C30 1713(3) 4133(3) 9848(2) 47(1) C31 1451(3) 4995(3) 9544(2) 42(1) C32 2201(3) 5587(3) 9411(1) 31(1) C33 2620(3) 10431(3) 9768(1) 25(1) C34 1581(3) 10579(3) 9640(2) 38(1) C35 649(3) 11250(3) 9888(2) 53(1) C36 740(4) 11787(3) 10258(2) 48(1) C37 1775(4) 11671(3) 10376(1) 38(1) C38 2709(3) 10993(2) 10135(1) 28(1) C39 8072(3) 10031(2) 8374(1) 24(1) C40 8563(3) 10128(3) 7886(1) 30(1) C41 9294(3) 10743(3) 7730(2) 37(1) C42 9510(3) 11299(3) 8064(2) 43(1) C43 9038(3) 11219(3) 8551(2) 44(1) C44 8328(3) 10578(3) 8708(1) 35(1)

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116 C45 5983(3) 5700(3) 7770(2) 42(1) C46 5668(4) 5357(3) 7383(2) 47(1) C47 4899(4) 6172(3) 7232(2) 42(1) C48 2260(3) 8408(3) 8672(2) 32(1) C49 1418(3) 8720(3) 8399(2) 35(1) C50 1962(3) 8592(3) 7923(2) 36(1) C51 5708(3) 9713(3) 7611(1) 29(1) C52 5486(3) 10089(3) 7151(1) 33(1) C53 4850(3) 9507(3) 7030(1) 31(1) Nd' 13538(1) 3349(1) 6665(1) 22(1) B' 14135(4) 2960(3) 7931(2) 28(1) N1' 13750(2) 1883(2) 6172(1) 22(1) N2' 14947(2) 3507(2) 5941(1) 25(1) N3' 12875(2) 5037(2) 6288(1) 26(1) N4' 11682(2) 3432(2) 6498(1) 25(1) N5' 15324(2) 2895(2) 7072(1) 30(1) N6' 15255(2) 2802(2) 7567(1) 30(1) N7' 13066(2) 4427(2) 7428(1) 29(1) N8' 13406(2) 4046(2) 7862(1) 28(1) N9' 13090(2) 2175(2) 7441(1) 26(1) N10' 13519(2) 2170(2) 7852(1) 25(1) C1' 12963(3) 1352(2) 6169(1) 21(1) C2' 13508(3) 455(2) 5889(1) 24(1) C3' 14584(3) 476(2) 5722(1) 24(1) C4' 14733(3) 1371(2) 5897(1) 21(1) C5' 15735(3) 1703(3) 5754(1) 25(1) C6' 15819(3) 2702(3) 5775(1) 26(1) C7' 16815(3) 3054(3) 5592(1) 36(1) C8' 16529(3) 4060(3) 5631(1) 38(1) C9' 15351(3) 4362(3) 5835(1) 29(1) C10' 14701(3) 5373(3) 5875(1) 29(1) C11' 13544(3) 5669(3) 6058(1) 29(1) C12' 12838(3) 6676(3) 6014(2) 38(1) C13' 11778(3) 6645(3) 6200(1) 35(1) C14' 11795(3) 5614(3) 6372(1) 28(1) C15' 10834(3) 5265(3) 6577(1) 26(1)

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117 C16' 10798(3) 4248(3) 6647(1) 26(1) C17' 9806(3) 3896(3) 6840(1) 31(1) C18' 10083(3) 2891(3) 6787(1) 31(1) C19' 11243(3) 2605(3) 6552(1) 24(1) C20' 11821(3) 1642(3) 6383(1) 22(1) C21' 16741(3) 937(3) 5521(1) 27(1) C22' 17304(3) 1112(3) 5050(2) 40(1) C23' 18244(3) 404(4) 4839(2) 50(1) C24' 18633(3) -482(4) 5092(2) 50(1) C25' 18080(3) -680(3) 5560(2) 44(1) C26' 17146(3) 29(3) 5774(1) 32(1) C27' 15273(3) 6186(3) 5657(1) 30(1) C28' 15253(3) 6986(3) 5931(2) 39(1) C29' 15803(3) 7725(3) 5719(2) 45(1) C30' 16357(4) 7680(3) 5246(2) 49(1) C31' 16379(3) 6907(3) 4967(2) 48(1) C32' 15821(3) 6167(3) 5172(1) 40(1) C33' 9736(3) 6046(3) 6692(1) 30(1) C34' 9523(3) 6702(3) 7058(1) 35(1) C35' 8473(3) 7398(3) 7164(2) 43(1) C36' 7667(3) 7449(3) 6901(2) 50(1) C37' 7870(4) 6799(3) 6529(2) 61(1) C38' 8897(3) 6094(3) 6423(2) 49(1) C39' 11152(3) 875(3) 6407(1) 24(1) C40' 11491(3) -88(3) 6626(1) 30(1) C41' 10855(3) -780(3) 6659(1) 39(1) C42' 9882(3) -540(3) 6481(2) 43(1) C43' 9541(3) 416(3) 6256(2) 42(1) C44' 10177(3) 1108(3) 6217(1) 32(1) C45' 16415(3) 2701(3) 6876(2) 42(1) C46' 17047(3) 2478(4) 7241(2) 63(2) C47' 16285(3) 2552(3) 7675(2) 50(1) C48' 12497(3) 5392(3) 7511(2) 33(1) C49' 12480(3) 5629(3) 7979(2) 39(1) C50' 13063(3) 4761(3) 8192(2) 38(1) C51' 12624(3) 1388(3) 7513(1) 28(1)

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118 C52' 12752(3) 883(3) 7963(1) 29(1) C53' 13332(3) 1393(3) 8166(1) 29(1) C90 10320(9) 6735(9) 5103(4) 89(4) C91 9865(7) 6354(6) 4726(3) 153(3) C92 9489(6) 5325(6) 4912(3) 164(4) Information for the crystal structure of 13 Table 1. Crystal data and structure refinement for 13 Identification code ak07 Empirical formula C66 H62 N5 O2 Yb Formula weight 1130.25 Temperature 173(2) K Wavelength 0.71073 Crystal system Triclinic Space group P-1 Unit cell dimensions a = 12.339(2) = 78.046(2). b = 14.745(2) = 88.104(3). c = 15.857(3) = 80.710(3). Volume 2785.4(8) 3 Z 2 Density (calculated) 1.348 Mg/m3 Absorption coefficient 1.728 mm-1 F(000) 1158 Crystal size 0.27 x 0.13 x 0.08 mm3 Theta range for data collection 1.31 to 27.50. Index ranges -16h15, -18k19, -20l20 Reflections collected 24756 Independent reflections 12365 [R(int) = 0.0372] Completeness to theta = 27.50 96.8 % Absorption correction Integration Max. and min. transmission 0.8860 and 0.6757 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 12365 / 0 / 585 Goodness-of-fit on F2 0.950 Final R indices [I>2sigma(I)] R1 = 0.0398, wR2 = 0.0920 [9866] R indices (all data) R1 = 0.0502, wR2 = 0.0943

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119 Largest diff. peak and hole 3.632 and -0.908 e.-3 R1 = (||Fo| |Fc||) / |Fo| wR2 = [[w(Fo2 Fc2)2] / [wFo22]]1/2 S = [[w(Fo2 Fc2)2] / (n-p)]1/2 w= 1/[2(Fo2)+(m*p) 2 +n*p], p = [max(Fo2,0)+ 2* Fc2]/3, m & n are constants. Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (2x 103) for 13. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________ x y z U(eq) ________________________________________________________________________ Yb1 3251(1) 3110(1) 3381(1) 34(1) O1 2603(2) 4461(2) 2571(2) 42(1) O2 1534(3) 2684(2) 3074(2) 60(1) N1 4344(3) 1640(2) 3533(2) 40(1) N2 2686(2) 2293(2) 4710(2) 34(1) N3 3338(2) 4136(2) 4308(2) 32(1) N4 4998(2) 3490(2) 3130(2) 36(1) N5 3479(3) 3079(3) 1790(2) 54(1) C1 5259(3) 1436(2) 3054(3) 47(1) C2 5380(4) 464(3) 2979(3) 63(1) C3 4567(4) 92(3) 3434(3) 57(1) C4 3924(3) 813(2) 3808(3) 42(1) C5 3076(3) 688(2) 4411(2) 39(1) C6 2563(3) 1361(2) 4869(2) 36(1) C7 1875(3) 1168(2) 5616(2) 42(1) C8 1602(3) 1967(2) 5905(2) 41(1) C9 2093(3) 2679(2) 5337(2) 35(1) C10 2004(3) 3610(2) 5429(2) 35(1) C11 2581(3) 4282(2) 4942(2) 33(1) C12 2488(3) 5240(2) 5049(2) 38(1) C13 3182(3) 5664(2) 4484(2) 38(1) C14 3744(3) 4961(2) 4030(2) 32(1)

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120 C15 4608(3) 5091(2) 3443(2) 32(1) C16 5223(3) 4383(2) 3073(2) 34(1) C17 6252(3) 4460(3) 2625(2) 41(1) C18 6634(3) 3625(2) 2430(2) 42(1) C19 5857(3) 3012(2) 2737(2) 39(1) C20 5956(3) 2067(2) 2679(3) 46(1) C21 2728(3) -264(2) 4640(3) 41(1) C22 3471(4) -1070(2) 4980(3) 47(1) C23 3134(4) -1941(3) 5184(3) 57(1) C24 2057(5) -2013(3) 5062(3) 69(2) C25 1316(4) -1235(3) 4746(4) 66(1) C26 1646(3) -353(3) 4532(3) 53(1) C27 1284(3) 3895(2) 6138(2) 37(1) C28 1734(3) 3963(3) 6899(3) 55(1) C29 1078(4) 4232(4) 7553(3) 69(1) C30 -36(4) 4426(3) 7454(3) 59(1) C31 -501(4) 4359(3) 6706(3) 54(1) C32 160(3) 4091(3) 6049(3) 48(1) C33 4924(3) 6051(2) 3202(2) 35(1) C34 4921(4) 6496(2) 2337(2) 45(1) C35 5224(4) 7381(3) 2103(3) 59(1) C36 5516(4) 7832(3) 2718(3) 57(1) C37 5501(3) 7406(3) 3567(3) 50(1) C38 5223(3) 6508(2) 3817(3) 40(1) C39 6952(4) 1679(3) 2212(3) 62(1) C40 7788(5) 1059(4) 2678(5) 113(3) C41 8709(7) 664(5) 2265(6) 155(4) C42 8790(7) 913(4) 1397(6) 134(4) C43 7980(6) 1543(4) 922(4) 98(2) C44 7062(5) 1921(3) 1345(4) 74(2) C45 3848(5) 2395(4) 1377(4) 79(2) C46 4131(6) 2569(6) 503(4) 106(2) C47 4043(6) 3466(7) 52(4) 119(3) C48 3623(5) 4226(5) 431(3) 85(2) C49 3467(6) 5171(6) 16(4) 111(3) C50 3024(6) 5844(5) 455(4) 107(2)

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121 C51 2717(4) 5629(4) 1319(3) 70(1) C52 2872(3) 4703(3) 1770(3) 48(1) C53 3329(4) 3987(4) 1313(3) 56(1) C54 573(4) 2903(5) 3544(4) 96(2) C55 -389(5) 3015(5) 3018(5) 117(3) C56 180(15) 2135(14) 2566(13) 152(8) C57 1309(9) 2173(8) 2450(7) 74(3) C56' -151(9) 3120(8) 2220(7) 65(3) C57' 974(16) 2929(17) 2197(13) 142(7) Information for the crystal structure of 27 Table 1. Crystal data and structure refinement for 27 Identification code ak06 Empirical formula C49 H51 Co N8 O9 P3 Pr Formula weight 1188.73 Temperature 173(2) K Wavelength 0.71073 Crystal system Orthorhombic Space group Pnma Unit cell dimensions a = 15.7281(7) = 90. b = 22.3431(11) = 90. c = 14.0630(6) = 90. Volume 4941.9(4) 3 Z 4 Density (calculated) 1.598 Mg/m3 Absorption coefficient 1.472 mm-1 F(000) 2416 Crystal size 0.18 x 0.08 x 0.08 mm3 Theta range for data collection 1.71 to 27.49. Index ranges -8h20, -29k12, -18l13 Reflections collected 18773 Independent reflections 5793 [R(int) = 0.0668] Completeness to theta = 27.49 99.4 % Absorption correction Integration Max. and min. transmission 0.8955 and 0.7901 Refinement method Full-matrix least-squares on F2

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122 Data / restraints / parameters 5793 / 0 / 374 Goodness-of-fit on F2 0.803 Final R indices [I>2sigma(I)] R1 = 0.0346, wR2 = 0.0545 [3452] R indices (all data) R1 = 0.0744, wR2 = 0.0586 Largest diff. peak and hole 0.812 and -0.549 e.-3 R1 = (||Fo| |Fc||) / |Fo| wR2 = [[w(Fo2 Fc2)2] / [wFo22]]1/2 S = [[w(Fo2 Fc2)2] / (n-p)]1/2 w= 1/[2(Fo2)+(m*p) 2 +n*p], p = [max(Fo2,0)+ 2* Fc2]/3, m & n are constants. Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (2x 103) for 27. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________ x y z U(eq) ________________________________________________________________________ Pr1 1020(1) 2500 4190(1) 20(1) Co1 3468(1) 2500 5528(1) 22(1) P1 2328(1) 2862(1) 6202(1) 22(1) P2 2762(1) 3310(1) 5158(1) 24(1) P3 3190(1) 2943(1) 4184(1) 26(1) O1 2340(6) 2500 7277(6) 18(2) O1' 2346(7) 2719(4) 7264(8) 13(2) O2 1463(2) 2735(2) 5768(2) 23(1) O3 2055(3) 3248(2) 4426(3) 22(1) O4 2273(3) 3075(2) 3936(3) 29(1) O5 3619(2) 2500 3378(2) 44(1) O6 3363(3) 3860(2) 4837(3) 40(2) O6' 3720(3) 3545(3) 4058(4) 40(2) O7 2399(1) 3578(1) 6220(2) 38(1) N1 -915(2) 2500 5773(2) 19(1) N2 -214(2) 3129(1) 4602(2) 20(1) N3 68(2) 4010(1) 3636(2) 26(1) N4 608(2) 3128(1) 2821(2) 22(1)

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123 N5 1156(2) 2500 1550(2) 27(1) C1 -719(2) 3026(1) 5383(2) 20(1) C2 -1062(2) 3592(1) 5729(2) 21(1) C3 -1566(2) 3741(2) 6505(2) 27(1) C4 -1761(2) 4337(2) 6642(2) 33(1) C5 -1480(2) 4778(2) 6011(2) 36(1) C6 -990(2) 4630(1) 5227(2) 31(1) C7 -774(2) 4034(1) 5096(2) 23(1) C8 -263(2) 3724(1) 4387(2) 22(1) C9 456(2) 3722(2) 2916(2) 25(1) C10 763(2) 4036(2) 2068(2) 30(1) C11 759(2) 4639(2) 1808(2) 44(1) C12 1125(3) 4788(2) 948(3) 63(1) C13 1474(3) 4352(2) 362(3) 64(1) C14 1464(2) 3753(2) 609(2) 47(1) C15 1097(2) 3597(2) 1473(2) 29(1) C16 963(2) 3026(2) 1952(2) 26(1) C17 3414(5) 2348(4) 2321(4) 37(4) C18 3213(6) 2940(4) 1910(6) 63(3) C19 3769(6) 3913(4) 3974(5) 60(3) C19' 3350(7) 4122(5) 3866(7) 56(3) C20 3390(6) 4342(5) 3317(7) 75(3) C20' 3178(6) 4248(5) 2918(6) 51(3) C21 1773(2) 4031(2) 6060(2) 38(1) C22 1094(2) 4020(2) 6800(2) 57(1) C23 1622(14) 2808(9) 7882(14) 30(7) C23' 1649(11) 2671(7) 7913(12) 15(6) C24 1798(14) 2500 8803(14) 46(6) C24' 1796(15) 2291(8) 8735(15) 31(4) C25 4170(3) 2500 6800(3) 29(1) C26 4369(2) 3008(2) 6254(2) 35(1) C27 4699(2) 2813(2) 5382(2) 42(1)

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BIOGRAPHICAL SKETCH Alison Steele Knefely, daughter of George and Carolyn Knefely, is a native of Pensacola, FL. She attended the International Baccelaurate (IB) program at Pensacola High School (PHS) from 1992-1996 and was captain of the girls tennis team. After graduating from PHS with an IB diploma, she attented Eckerd College (EC), in St. Petersburg, FL, from 1996 to 2000. At EC, Alison was the captain of the womens tennis team and a chemistry major. While at EC, she had the opportunity to conduct research under the advisement of Dr. R. Chris Schanbel at EC and Los Alamos National Laboratory (LANL), and under the advisement of Dr. Mike Scott at the University of Florida (UF) in Gainesville, FL and Dr. Marcel Wesolek at the University of Louis Pasteur in Strasbourg, France. After graduating from EC with a BS in Chemistry, Alison started graduate school at UF. She became a member of Jim Boncellas group in October 2000 and had the opportunity to conduct research under his advisement at UF and LANL. After graduating from UF, Alison and her husband, Rob, will move to the Philadelphia area. 131


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SYNTHESIS AND CHARACTERIZATION OF LANTHANIDE COMPLEXES FOR
USE IN NEAR-INFRARED LIGHT EMITTING DIODES















By

ALISON STEELE KNEFELY


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


2005

































This document is dedicated to my grandparents RADM and Mrs. Richard A. Paddock
and Mr. and Mrs. George M. Knefely, Sr., my parents Dr. and Mrs. George M. Knefely,
Jr. and my loving husband Charles Robert Sides.















ACKNOWLEDGMENTS

First of all, I would like to thank my advisor, Jim Boncella, for all of his guidance,

understanding and support throughout my graduate career. I would like to also thank him

for the opportunity to work at Los Alamos National Lab, where I had the privilege to

meet and work with other great scientists. I would like to thank Tony Burrell for taking

me under his wing at LANL and for sharing his knowledge of porphyrin chemistry and

electrochemistry. I would like to thank all the people who made it a smooth transfer to

and from the lab, especially Bill Tumas, Bev Ortiz and Deb Allison-Truijillo. I would

like to thank my dear friends and colleagues, especially Edel Minogue, Paul and Isabel

Plieger, Gavin Collis, Piyush Shulka and the Burrell and Boncella families who not only

helped in chemistry, but made me a part a family, provided tennis partners and made

living in Los Alamos enjoyable and memorable.

I would like to thank Kirk Schanze and all the members of the group who provided

a bench, hood, desk and a group of great people with whom to work. I would like to

thank Lisa McElwee-White and all of the group members who provided a glove box and

solvent system for me to use. I would like to thank the former members of the Boncella

group, especially Elon Ison, Tim Foley and Tom Cameron, for all of their friendship and

guidance. I would like to thank all the collaborators who have come together to make

this work possible, especially Khalil Abboud, Brian Scott, John Reynolds, Paul

Holloway, Ben Harrison, Garry Cunningham, T.S. King, Nisha Ananthakrishnan and

Fengui Guo. I would like to thank my undergraduate research advisor, R. Chris









Schnabel. Without his love for chemistry, I would not have developed a taste for

synthetic chemistry and without his guidance, I would not have pursued a career in

chemistry.

I would like to thank my parents whose love and support have carried me through

all of these years. I thank my entire family, the Knefelys, Paddocks, Stumpfs and Sides,

for all of their encouragement. Finally, I would like to thank my husband Rob for giving

me the love, strength and laughter to finish and make it a fun ride.
















TABLE OF CONTENTS

page

A C K N O W L E D G M E N T S ................................................................................................. iii

T A B L E ...................v...................i...................i.........i

LIST OF FIGURES ......... ........................................... ............ ix

A B S T R A C T .......................................... .................................................. x iii

CHAPTER

1 IN T R O D U C T IO N ............................................................................. .............. ...

2 LANTHANIDE TETRAPHENYLPORPHYRIN COMPLEXES: SYNTHESIS,
CHARACTERIZATION AND LUMINESCENCE STUDIES...............................11

Introduction .................. ...................................................... ........ ...... 11
Previous Synthetic Procedures ............................................................................12
Synthesis of N d and Pr Com plexes ........................................ ........................ 14
H alf-Sandw ich Com plexes ........................................................ ............... 14
LnTPPI(DM E) Com plexes...................................................................... 16
L nTPP(L ) C om plexes................................................. ............................. 18
LnTPP(Tp) com plexes ........................................ ........................... 19
LnTPP(LOEt) complexes........................... .................. ............... 21
LnTPP(quinolate) complexes............... ...................... .. ............... 23
N M R Studies ................................................................... 24
N dT PP T p .................................................................................................. ........25
N dTPP(LOEt) ............... .. .... ....... ....... ...... ... ........... ...... ........ ......29
LnTPP(L) Photoluminescence and Electroluminescene Studies...............................32
Sum m ary and C onclu sions .............................................................. .....................35
E xperim mental ................................................... ................................ 36
M materials and R eagents................................................ ............................ 36
S y n th e sis ........................................................................................................ 3 7
N dI3(TH F)4 (1) ................................................................ ........37
PrI3(TH F)4 (2) ..................... ......... ............ .............. ............... 38
N dTPPI(D M E ) (3)........................ .................. ................ .............. 38
PrTPPI(DM E) (4) .................................... ...............................39
G dTPP(C1)D M E (5) .............................................................................. 39
L uTPP(C 1)D M E (6)........................................................... ............... 39


v









N dT P P T p (7) ................................................................................. 40
P rT P P T p (8 ) ........................................................................................... 4 0
GdTPPTp (9) .............. ..... ..................................41
L u T P P T p (10) ...........................................................4 1
N dTPP(LO Et) (11) ....................................... ................... ............... 42
PrTPP(LO Et) (12) ......................................................... 42
Y b T pp Q (T H F ) (13)................................................................................ 4 3
X -ra y .................................................................................................................... 4 3
N d T P P I(TH F )2 ....................................................................................... 4 3
L u T P P C (D M E ) ..................................................................................... 4 4
N d T P P T P ............................................................................................... 4 5
Y bT ppQ (T H F ) ..........................................................46

3 LANTHANIDE SUBSTITUTED TETRA(ARYL)PORPHYRIN AND
PHTHALOCYANINE COMPLEXES : SYNTHESIS, CHARACTERIZATION
AND LUM INESCENCE STUDIES ....................................................... 47

Substituted Tetra(aryl)porphyrins............................... .........47
Synthesis .............................................. 48
N M R S tu d ie s ................................................................................................. 5 0
Electrochem istry .......................................... ................ ..... .......... 52
Photoluminescence and Electroluminescene Studies .......................................61
Summary ............................................................ ................ 63
Lanthanide-Phthalocyanine Complexes .......................... ........ ...............63
Synthesis and Structure of LnPc(LOEt) Complexes .............. ............ 64
N M R S tu d ie s ................................................................................................. 6 7
Photolum inescence Studies ....................................................... 68
Sum m ary ................................................................................................... ....... 69
E x p erim mental .................. .................................................................................6 9
M materials and R eagants................................................... 69
Synthesis..................................... ........ 70
Yb(TMPP)CI(DME) (14) ..................................70
Yb(TMPP)Tp (15)................................................ 71
4(2-ethylhexyloxy)benzaldehyde (16)96.............................. ...................71
5,10,15,20-tetrakis [4-(2-ethylhexyloxy) phenyl]-porphyrin (TPPoeh)
(17)....................................................... 72
Li2TPPoeh(DME)4 (18) ............................................................... ................ 72
Y bTPPoehC I(D M E) (19) ....................................................... 73
Y b T P P oeh (T p) (2 0)................................................................................ 73
Li2TPyP(DMF)2 (21) ........... .............................74
Y bTPyPC I(D M E) (22) ....................................................... 74
YbTPyP(LOEt) (23) ... ............................................... ........ .. .. ...... .... 75
N dP cI(D M E ) (24) .............................................. .................................75
P rP cI(D M E ) (2 5)............ ................................ .......... .......... ... ......... 76
N dPc(LOEt) (26) .................. ............................. ........... ............ 76
PrPc(LOEt) (27) .......................... ....... .. ................... 76
H oP c(L O E t) (28)............. .................................. ........ ........ ... ......... 77









T m P c(L O E t) (29) ......................... .... .............. ....................... 77
XRA Y of PrPc(LOEt) ........................................................... ............... 78

4 POLYERMIZABLE LANTHANIDE-PORPHYRIN COMPLEXES .......................79

In tro d u ctio n ........................................................................................................... 7 9
Lanthanide Polym ers ............................................ ...... ..... ............ 79
P orphy rin P oly m ers .................................................................. .....................80
Lanthanide-Porphyrin Polymer Complexes .................................... ...............82
Lanthanide-vinylporphyrin Complexes............................................................82
S y n th e sis ................................................................................................. 8 2
N M R stu d ie s ........................................................................................... 8 6
M etathesis reactions ........................... ...... .............. .... ........ .. ...... .. 88
P olym erization ....................... .. .... ................... .... .. ........... 93
Tp Polymer .............. ..... ......... ....................................... 95
Sum m ary ................ ..................................... ........................... 97
Experimental .............................. .. .. ...... .......... ............. 99
M materials and R eagents................................................ ............................ 99
S y n th e sis ............................. ...................................................... ............... 10 0
T P P v (30) ....................................................................100
L i2T PP v(D M E )2 (3 1)...................................................................... .. .... 10 1
Y bTPPvC1(D M E) (32) ........................................ .......................... 101
Y bT PP v(T p) (33) ............................................. ...................... ........... 102
Y bTPPv(L O E t) (34) .............................................................. ............... 102
T PP -T P P (35) ................................................................. 103
YbTPPTp-Y bTPPTp (36) ........................................ ....... ............... 103
Y bTPP-Tp polym er (37) ........................................ ........................ 104
Copolymerizations ..........................................................................104

5 CONCLUSIONS ..................................... .. ........ ..............106

C rystallographic inform action ......................................... ................................. ...... 10

L IST O F R EFER EN CE S ....................... ................. .............................. ............... 124

BIOGRAPH ICAL SKETCH ....................... .......... ........................................... 131
















TABLE


Table page

Table 3.1: Half wave potentials and band gaps of Ln-porphyrin complexes (potentials
are reported vs Fc/Fc+ internal standard). ..................................... ............... 61















LIST OF FIGURES


Figure p

1.1: Examples of compounds used as emitters in OLEDs.2 .............................................1

1.2: Configuration of multi-layer device and molecular structures..............................2

1.3: Configuration of a typical multi-layer device. ........................................ ..............4

1.4: Common organic molecules for hole and electron transport. ..................................5

1.5: Commonly used conjugated polymers for emission in device construction.............5

1.6: Scheme of Dexter and Forster energy transfer mechanisms..............................6

1.7: Ir(acac) dopants for O LED s. .......................................................... .....................7

1.8: Energy transfer from chromophore to lanthanide metal center for sensitized
em mission ............. ..................................................................... ..................

1.9: Normalized luminescence of Yb3+, Nd3+, Er3+, Ho3 and Tm3+.24.....................9

2.1: Synthesis of LnTPPCl(DME) where Ln = Ho, Er, Tm, and Yb. ..........................13

2.2: Synthesis of LnTPP(L) complexes (Ln= Ho, Er, Tm,Yb and L= Tp,L(OEt))........14

2.3: Synthesis of N dTpCl2(TH F)2. ...................................................... .....................15

2.4 : Synthesis of 3 and 4. ........................ ...................... ... .. ....... .... ...........16

2.5: Thermal ellipsoid plots of the molecular structure of NdTPPI(DME) (top) and
LuTPPCl(DME) (6) (bottom), showing selected atom labels, drawn at the 50 %
probability level. The hydrogen atoms have been excluded for clarity .................18

2.6: Synthesis of LnTPP(Tp) where Ln = Pr, Nd, Gd, Lu............... ........................20

2.7: Thermal ellipsoid plot of NdTPPTp (7) showing selected atom labels drawn at
the 50 % probability level. The hydrogen atoms have been excluded for clarity. ...21

2.8: Synthesis of LnTPP(LOEt), where Ln = Nd (11), Pr (12). ...............................22

2.9: Synthesis of YbTPP(Q)TH F (13)....................................... ......................... 23









2.10: Thermal ellipsoid plot of YbTPP(Q)THF (13) showing selected atom labels
drawn at the 50 % probability level. The hydrogen atoms have been excluded
for clarity .............................................................................24

2.11: 1H N M R ofN dTPPTp (7). ........................................................... .....................26

2.12: Variable temperature NMR of the phenyl region of NdTPPTp (7) from 20-50. .27

2.13: Full COSY NMR ofNdTPPTp (7) (top), expansion from 8.5-5.5 ppm (bottom). .28

2.14: H NM R spectrum of NdTPP(LOEt) (11).................................... ..................30

2.15: COSY NM R of NdTPP(LOEt) (11)................... ............................................ 31

2.16: COSY NMR of NdTPP(LOEt) (11), expansion from 8-2ppm. ............................31

2.17: PL emission NdTPPL (solid lines, L = Tp, dashed lines, L = LOEt). ....................32

2.18: Device architecture................... ...... .... .............. ....... 33

2.19: C charge hopping cartoon. ............................................... ...................................34

2.20: Electroluminescence emission of Ln(TPP)(LOEt) in polystyrene measured at 9
V. Ln = Nd (solid line), Yb (dashed line) and Er (dotted line).74 .........................34

3.1: Synthesis of YbTmPP(C1)DME (14), YbTPPoeh(C1)DME (19), and
Y bTPyP(C1)D M E (22). ................................................ ................................ 48

3.2: Synthesis of Yb(TmPP)Tp (15), Yb(TPPoeh)Tp (20) and Yb(TPyP)L(OEt)3
(2 3 ) ................................................................................ 5 0

3.3: Proton NMR spectrum of Yb(TmPP)Cl(DME) (14) in DMSO-d6 (*)....................51

3.4: Proton NMR of Yb(TPyP)L(OEt)3 (23) in C6D6(* denotes silicon grease
im p u rity ) ...................................... ............................ ..... ....... ...... 5 2

3.5: 1-Butyl-1-methyl-pyrrolidium bis(trifluoromethyl)sulfonamide ([BMP+]-[NTF-
]), ionic liquid used for electrochemical studies. ............. ...................... ......... 53

3.6: Cyclic voltamogram of [BMP+]-[NTF-]......................... ......... ............53

3.7: CV of a reversible reduction and reoxidation. ........................................... 54

3.8: Electrode reaction mechanism of LnTPP(acac). ............... ............. ............... 55

3.9: CV of TmPP in ionic liquid with a scan rate of 0.1 V/s (* indicates Fc/Fc)..........55

3.10: Cyclic voltammogram of 15 in ionic liquid with a scan rate of 0.3 V/s (*
indicates F c/F c ) .......... ........................................................................ .......... 56









3.11: Cyclic voltammogram of TPyP in ionic liquid with a scan rate of 0.3 V/s. ...........57

3.12: Cyclic voltammogram of the oxidation (left) and reduction (right)
ofYbTPyP(LOEt) in ionic liquid with a scan rate of 0.3 V/s ...............................58

3.13: Cyclic voltammogram of YbTPPTp in ionic liquid with a scan rate of 0.2 V/s (*
in d icate s F c/F c+) ............. ......... .. .... ......... .. .... .................. ................ 5 8

3.14: Cyclic voltammogram ofYbTPP(LOEt) in ionic liquid with a scan rate of 0.05
V /s (* indicates F c/F c )......................................... .............................. .. 59

3.15: Electroluminescence of Yb(TMPP)TP (bottom), Yb(TPyP)L(OEt)3 (middle),
and Yb(TPPoeh)TP (top) as a function of increasing voltage, starting at 6 V to
20 V ........................................................................62

3.16: Phthalocyanine (Pc)................... .................... ............ 64

3.17: Synthesis of LnPcI(DME), Ln= Nd, Pr ...............................................65

3.18: Synthesis of LnPc(LOEt) complexes, Ln = Pr, Nd............... ...... ..................65

3.19: Solid state structure of PrPc(LOEt) (27). ..................... ......... ........... ..............66

3.20: H NMR spectrum of PrPc(LOEt) (27) ..................................... ...................67

3.21: COSY NMR spectra of PrPc(LOEt) (27)............................................................68

3.22: Expansion of COSY NMR spectra of PrPc(LOEt) (27). ........................................68

4.1: Eu(TTA)2(VBA)phen-NVK copolymer.......................................... .............80

4.2: Structure of porphyrin supported in polyaniline. ...................................................81

4.3: Examples of porphyrin polymers. ................................................. ................82

4.4: Synthesis of TPPv. ........................................... .. .... ......... ......... 83

4.5: Synthesis of vinylporphyrin by Pomogailo et al. ...............................................84

4 .6 : Synthesis of 32 ....................................................................... .............................. 85

4.7: Synthesis of complexes 33 and 34. .............................................. ............... 85

4.8: 1H NMR spectrum of YbTPPvTp (33).......... .. ...... ......... ..............86

4.9: COSY NMR of 33 (top), expansion from 11-6 ppm (bottom) ...............................87

4.10: Catalytic cycle for metathesis reaction between vinyl porphyrins..........................88









4.11: 1H NMR spectrum of 35 (aromatic region of 30 in inset) ...................................90

4.12: Synthesis of 36. ....................................... ......... ......... ........ ............... 91

4.13: 1H NMR spectrum of the phenyl region of 36 (33 in inset)........................ 92

4.14: 2-D NMR spectrum of the phenyl region of 36. ...................................................92

4.15: Scheme of a free radical chain growth mechanism.............................................. 93

4.16: Chem ical structures of m onom ers ........................................ ........ ............... 94

4.17: Structure of Tp polym er. ..... ........................... ........................................95

4.18: Synthesis of YbTPP-Tp (37) polymer....................................... ......... ............... 96

4.19: Absorption spectrum of 37 (inset shows Q bands). ............. ................................ 97

4.20: NIR emission spectrum of 37 ......... ......... ................. ........... .............. 97















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

SYNTHESIS AND CHARACTERIZATION OF LANTHANIDE COMPLEXES FOR
USE IN NEAR-INFRARED LIGHT EMITTING DIODES

By

Alison Steele Knefely

December 2005

Chair: James M. Boncella
Major Department: Chemistry

The synthesis and characterization of a series of new lanthanide porphyrin and

phthalocyanine complexes was investigated in order to study the luminescence properties

of these complexes for polymer light emitting diodes. These lanthanide complexes

consist of the near-infrared emitting lanthanides (Ln=Pr3+, Nd3+, Ho3+, Tm3+ Yb3+, a

macrocyclic chromophore to sensitize the emission of the lanthanide ion, and a capping

ligand to encapsulate and shield the lanthanide from solvent molecules that affect

emission efficiency. Lanthanide complexes were synthesized with a variety of

chromophores and capping ligands to study the effects of different molecules on device

efficiency.

The procedure to synthesize LnTPP(X)(DME) complexes provided a high yielding

approach to new lanthanide porphyrin complexes that serve as the starting material for a

variety of lanthanide-porphyrin complexes via a salt metathesis reaction, replacing the

halide and solvent molecules with multidentate ancillary ligands. Lanthanide









monoporphyrinate complexes, LnTPP (TPP=tetraphenylporphyrin) were synthesized and

characterized with the capping ligands hydrotris(pyrazolyl)borate (Tp),

(cyclopentadienyl)tris(diethylphosphinito)cobalt(I), K(LOEt), and (hydroxy)quinolate

(Q) to study the effects of capping ligands on device efficiency. Effects of varying the

chromophore were also studied with the synthesis of lanthanide complexes of tetra(2,3,4-

trimethoxyphenyl)porphyrin (TmPP), tetra(4-pyridyl)porphyrin (TPyP), tetra(3-

ethylhexyloxypheny)porphyrin (TPPoeh) and phthalocyanine (Pc). These complexes

were isolated in high yields and characterized by 1-D and 2-D NMR spectroscopy,

UV/Vis spectroscopy and elemental anaylsis. Photoluminescent studies on

Ln(porphyrin)L complexes showed NIR emission with quantum efficiencies ranging

from 4.1%-0.91%. Electroluminescent studies using devices blended with polystyrene

and Ln(porphyrin)L complexes produced NIR emission with quantum efficiencies

ranging from 0.01%- 0.03%.

Studies were then conducted on the effects of incorporating the Ln-porphyrin

complex into a polymer backbone. A ytterbium-vinylporphyrin complex was

copolymerized with t-butylstyrene and trifluoroethyl methacrylate to give a copolymer

with 1 mol% of the lanthanide complex and a weight average molecular weight (Mw) and

a number average molecular weight (Mn) of- 200,000 and 90,000, respectively.

Polymers containing trispyrazole borate (Tp) units were synthesized by Prof Frieder

Jaekle's group, at Rutgers University, and yielded the Yb-TPP incorporated polymer.

Absorption and NIR emission studies showed typical LnTPP absorption and Yb-

emission.














CHAPTER 1
INTRODUCTION

Organic and polymeric light emitting diodes (OLEDs and PLEDs) represent a

rapidly growing field as industry and academia pursue the development of new,

inexpensive, durable, flexible and efficient light sources. These materials are able to

produce light through electroluminescence, a process in which an applied electric field

generates an excited species that radiatively decays. Research has developed OLEDs and

PLEDs that produce light across the entire visible region with device efficiency,

brightness and lifetime rapidly approaching commercial target figures (Figure 1.1).1



N CF3

Al N




400nm 500nm 600nm 700nm






S/NC





Figure 1.1: Examples of compounds used as emitters in OLEDs.2









The first efficient electroluminescence from an organic solid was demonstrated in

the early 1960s using anthracene crystals.3 Crystals 1-5 mm thick emitted blue light with

quantum efficiencies 8%, but with operating voltages between 50-1000 V.4

Improvement in device construction and operation occurred in 1987 with the construction

of the first vacuum deposited multi-layer device.5 The device consisted of a double layer

of organic thin film, with one layer capable of only monopolar transport and the other

layer capable of luminescence. Devices using an aromatic diamine as the first organic

layer and 8-hydroxyquinoline aluminum (AlQ3) as the luminescent material produced

high brightness green light with voltages as low as -10 V (Figure 1.2).





MgAg cathode -\ / N \

Alq3 l
AlqAlq3
+_Diamine Alq3

Indium-Tin-Oxide (ITO) anode

Glass






Diamine
Figure 1.2: Configuration of multi-layer device and molecular structures.

Since the development of organic thin film electroluminescence by Tang in the

1980s,6 there has been much interest in organic, as well as conjugated polymer (CP) thin

films as new materials for light emitting diodes (LEDs). With the construction of a









device using poly(p-phenylene vinylene), Borroughes et al. showed that polymeric thin

films can produce efficient devices. Polymer based LEDs (PLEDs) have many

advantages over current inorganic devices such as low costs, easy processing and the

ability to emit in wavelengths that span the visible spectrum.8

The simplest device configuration consists of a single organic/polymeric layer in

between an anode and a cathode. With an applied electric field, holes from the anode and

electrons from the cathode are driven into the emissive layer, where they recombine to

form an excited state of the polymer that decays either radiatively or non-radiatively.

The cathode is a low work function material that injects electrons into the lowest

unoccupied molecular orbital (LUMO) of the emissive layer and is typically a metal such

as calcium, magnesium, or aluminum. The anode is a high work function material that

injects holes into the highest occupied molecular orbital (HOMO) of the emissive layer.

Indium-tin-oxide (ITO) is a commonly used anode because of its good transmission

properties over the desired wavelength range.

In a single layer device, the organic/polymeric layer serves as the emitting source

as well as the charge carrier and should therefore have high photoluminescence quantum

efficiency and the ability to transport holes and electrons. Single layered devices,

however, exhibit low quantum efficiencies and short operational lifetimes caused by

enhanced quenching at the electrode-organic interface as well as deterioration of the

organic layers.4'9 Because a single material having all the necessary properties for

optimal device performance does not exist, additional layers can be added to the LED to

improve the charge transport, quantum efficiency of emission and stability of the

device.10 A typical multilayer device is comprised of an anode (ITO), a hole transport









layer, emitting layer, electron transport layer and a cathode (Figure 1.3). More elaborate

device construction strategies have also been used.



Cathode
S-- Electron Transport Layer

S0 0 -- Emitting Layer

Anode (ITO) Hole Trasnport Layer

Glass substrate-



Figure 1.3: Configuration of a typical multi-layer device.

An effective hole-transport layer should have a low ionization potential for efficient

injection of holes from the anode, a higher exciton energy level than the emissive layer

for confining excitons within the emissive layer and should be transparent to the radiation

emitted from the device.10 A commonly used polymer is poly(3,4-

ethylenedioxythiophene) doped with polystyrene sulfonic acid (Figure 1.4). The

introduction of an electron-transport layer helps control charge injection, transport, and

recombination in the emissive layer of the device. The electron transport material should

have a high ionization potential to efficiently block holes and high electron mobility to

transport electrons to the emissive layer. Oxadiazoles such as 2-(4-biphenyl)-5-(4-t-

butylphenyl)-1,3,4-oxidiazole (PBD) and metal chelates such as AlQ3 are the most

widely used electron transport materials (Figure 1.4).11

Conjugated polymers (CP) typically used for emission include a yellow-green

emitter poly(p-phenylene vinylene) (PPV), the first CP used in a PLED,7 an orange-red









emitter poly(2-(2'-ethylhexyloxy)-5methoxy-1,4-phenylene vinylene) (MEH-PPV) and a

blue emitter poly(p-phenylene) derivative, PPP-OR11 (Figure 1.5).


0 0 0 0 n m




O O SO3 SO3H

PEDOT PSS








PBD

Figure 1.4: Common organic molecules for hole and electron transport.





0 O O0
0 /3



/\ n
Meo n O

013 n
PPV MEH-PPV PPP-OR11

Figure 1.5: Commonly used conjugated polymers for emission in device construction.

While there has been much research devoted to the improvement of the

luminescence and efficiencies of PLEDs, there are some inherent problems with pure

PLEDs. When recombination occurs, the spin wave function (S) of the excited molecule









can either be a singlet (S=0) or triplet (S=1). In organic materials, the triplet state decays

non-radiatively.1 Statistically, 75% of injected charges are in the triplet state, limiting

organic device efficiencies to about 25%.10 Another problem is that CPs have broad

emission spectra, with a typical full width at half max of 50-200 nm,12 which gives rise to

poor color purity. Consequently, PLEDs do not have the ability to produce finely tuned

emission with maximum efficiencies.

In order to combat these problems of pure PLEDs, recent work has focused on

blending polymers with materials with significant spin-orbit coupling, which facilitates

inter-system crossing and allows triplet state emission. Organometallic compounds have

been found to be prime examples of good triplet state emitters and therefore successful

dopants for polymer devices. The dopant can harvest energy from the polymer by Forster

energy transfer (induced dipole mechanism) or Dexter energy transfer (an electron

exchange mechanism) (Figure 1.6) or direct charge trapping and exciton formation on the

dopant itself.2'13 Efficient energy transfer from host to dopant depends on the quantum

yield of emission by the donor (D*), the light absorbing ability of the acceptor (A) and

the overlap of the emission spectrum of D* and the absorption spectrum of A.


D* A
D* A


D


A*
A*


A D*
A D*


Dexter Energy Transfer Forster Energy Transfer

Figure 1.6: Scheme of Dexter and Forster energy transfer mechanisms.

Recently published reports show that devices constructed with blends of platinum

(Pt) and iridium (Ir) complexes have high luminescence effieciences with the ability to









tune the emission color through much of the visible region by simply changing the

ligands of the complex.1 Thompson and coworkers have synthesized a series of Ir-

(acetylacetonate) complexes that give green, yellow and red electroluminescence with

external quantum efficiencies ranging from 6%-12% (Figure 1.7).14






S\ N V T
0 DN 0


0\ O S


_20 2
2


ppy2Ir(acac) bt2Ir(acac) btp2Ir(acac)
Green Yellow Red

Figure 1.7: Ir(acac) dopants for OLEDs.

With unique optical properties such as line like emission, long luminescence

lifetimes and a wide spectral range (from blue to near-infrared), the trivalent lanthanides

have also been used as dopants in LEDs.15 The optical properties are governed by the 4f-

orbitals, which are shielded from external forces by the 5p and 5s orbitals. The 4f-orbials

only weakly interact with the ligands bound to the metal center, leading to small ligand

field splitting and thus sharp emission spectra at certain wavelengths regardless of the

ligand. Thef-ftransitions, however, are forbidden and consequently the lanthanides have

rather low molar absorptivity coefficients and must be sensitized to produce intense

emission. The process of sensitized emission,16 known as the antenna effect, begins with

the ligand absorbing energy, undergoing inter-system crossing from singlet to triplet state









and then transferring the energy to the lanthanide metal center (Figure 1.8). The excited

state of the antenna must, therefore, be higher in energy than the emissive level of the

lanthanide metal center.


S C
Si ___% C



ST1 Ln*


luminescence


So Ln
ligand

Figure 1.8: Energy transfer from chromophore to lanthanide metal center for sensitized
emission.

The first reports of devices using lanthanide complexes as the emitting species used

Eu(thenoyltrifluoroacetonate)3 (Eu(TTFA)3) and Tb(acac)3 to produce red and green

emission, respectively.17,18 Since these reports, there have been many studies examining

a variety of Tm3 complexes for blue light19 and Eu3+ and Tb3 complexes for sharp

emission of red, green and white light.10,20-23

Interest in NIR/IR emitting devices for such uses as telecommunication and sensors

has brought the blending of CPs with lanthanides to the attention of many research

groups including ours. Figure 1.9 shows the normalized luminescence spectra of the

near-infrared emitting lanthanides.


























_- II II I
800 1000 1200 1400 1600
\ A, nm /

Figure 1.9: Normalized luminescence of Yb3+, Nd3+, Er3+, Ho3+ and Tm3.24

Recent reports show NIR emission from devices made with blends of a CP and Er

(acetylacetonato)3(1,10-phenanthroline) to give 1.54 jtm emission25 and a Nd(lissamine)

complex to produce typical Nd3 luminescence at 890, 1060 and 1340 nm.26 The low -

lying radiative levels of the lanthanide ions are easily quenched by the vibrational energy

of O-H and C-H molecules from solvents or ligands; thus, ligands bound to the

lanthanides should not only contain a chromphore that can readily excite the lanthanide,

but should also encapsulate the ion to shield it from solvent molecules. In efforts to

improve device luminescence and efficiencies, our group has become interested in

synthesizing lanthanide complexes of nitrogen-based macrocycles for use in NIR LEDs.

The following chapters discuss the synthesis and characterization of a series of new

lanthanide porphyrin and phthalocyanine complexes. The use of these compounds in






10


PLED devices and the characterization of the performance of these devices are also

presented.














CHAPTER 2
LANTHANIDE TETRAPHENYLPORPHYRIN COMPLEXES: SYNTHESIS,
CHARACTERIZATION AND LUMINESCENCE STUDIES

Introduction

Porphyrins are interesting molecules because their large n systems give them

properties that allow them to be used in photodynamic therapy, areas of light harvesting,

catalysis and optics.27 As highly conjugated molecules, porphyrins are promising organic

molecules for the design of efficient luminescent materials. Forrest et al. have used

tetraphenylporphyrin (TPP) as the red emitter in light emitting diodes (LED),28'29 while

other groups have examined platinum porphyrin complexes as emissive dopants in

LEDs.12,29-32

The small absorption coefficients of the lanthanides make light absorption and

emission an inefficient process for these metal ions and require that sensitization by a

coordinating ligand be used for efficient light absorption and emission. Contributing

factors to the luminescence intensity are the intensity of the ligand absorption and the

efficiency of ligand-to-metal energy transfer.33 With a molar absorptivity -300,000 and

triplet energies typically around 12,000 cm-1-17,000 cm-1, studies show that TPP

efficiently absorbs light and transfers energy to the metal ions.34-36 These studies also

reveal that lanthanide-porphyrin complexes possess rapid rates of energy transfer from

the porphyrin to the lanthanide ion.

The intense Soret band of lanthanide porphyrin complexes leads to facile singlet

excitation, while the presence of the lanthanide ion gives rise to facile inter-system









crossing to the low energy triplet state that can readily excite the emissive states of the

lanathanide ion.37-39 Meanwhile, the highly delocalized 7t system of these complexes is

suitable for efficient hole-transport40'41 through the bulk material. This combination of

properties makes TPP a proficient ligand for energy transfer to near-infrared emitting

lanthanide ion.

Previous Synthetic Procedures

The first synthesis of lanthanide-monotetraphenylporphyrin (LnTPP) complexes

was reported by Wong et al. in 1974.42 Lanthanide-monoporphyrinate complexes have

been studied for their use as NMR shift reagents,42-44 and as probes in the area of clinical

and molecular biology,45'46 but difficulties in their syntheses have stunted the growth of

research in this field. As the accepted LnTPP synthesis, Wong's procedure involves the

reaction between Ln(acac)3 and the free base tetraphenylporphyrin (H2TPP) in refluxing

trichlorobenzene. While progress of the reaction monitored by UV/Vis spectroscopy

shows a yield of greater than 90%, the LnTPP(acac) compound is isolated by column

chromatography, leading to product decomposition and isolated yields of 10-30%. With

the use of this method, Yb- and Er-porphyrin complexes were synthesized and found to

be viable as NIR lumophores in NIR LEDs.39 These results stimulated our interest in

finding a high yielding synthetic procedure that would allow us to access complexes with

a variety of ligands that might have improved luminescent properties.

Since the first reported synthetic procedure for lanthanide monoporphyrinate

complexes, there have been few reports of new procedures that improve conditions or

yields with most research utilizing Wong's procedure.37'47-49 In 1999, an alternate

procedure generating a hydrated LnTPP(C1) complex was published.50 The disadvantage









of this synthetic procedure is that the complexes are coordinated to several equivalents of

water. Since the excited state of the lanthanide ion is effectively quenched by vibrational

energy transfer to solvents or ligands containing O-H groups, this synthetic procedure is

not amenable for use in near IR emissive systems.

Recently our lab has developed a high yielding synthetic procedure for lanthanide

tetraphenylporphyrin chloride complexes5 via a salt metathesis reaction between

tetraphenylporphyrin dianion and anhydrous LnC13. Reaction of these compounds in

refluxing toluene gave the lanthanide tetraphenylporphyrin chloride (LnTPPCl(DME)) in

yields greater than 75%. Progress of the reaction can be monitored by UV/Vis

spectrometry as the Soret band shifts from 417 nm of free TPP to 422 nm for

metalloporphyrin. The complexes are then easily isolated by simple filtration and

recrystallization. This synthetic approach was successfully applied to ytterbium, thulium,

erbium and holmium complexes (Figure 2.1).


--I o
C1-Ln- n O
N










Ln= Ho, Er, Tm, Yb
Figure 2.1: Synthesis of LnTPPCl(DME) where Ln = Ho, Er, Tm, and Yb.

These complexes were then used to synthesize a series of sterically saturated

monoporphyrinate lanthanide complexes via a second salt metathesis reaction, replacing

the chloride ion and solvent molecule with an ancillary ligand (Figure 2.2). Addition of










potassium acetylacetonate to the Yb complex in dimethoxyethane gave the YbTPP(acac)

complex in yields greater than 90%.


SEtO OEt
SEtO--P--Co--P-OEt
N tO
N NKTp, K(LOEt)
ol K(LOEt), to0
Lin DME Cl-ln-0 THF
rt, 12h rt, 12h n
Ph
Ph Ph Ph" PhPh Ph
N N N

N N N N N N

Ph N Ph Ph N Ph Ph N Ph



Ln Ho, Er, Tm, Yb
Figure 2.2: Synthesis of LnTPP(L) complexes (Ln= Ho, Er, Tm,Yb and L= Tp,L(OEt)).

Synthesis of Nd and Pr Complexes

In order to complete the series of near-IR emitting lanthanides, the same synthetic

routes used to synthesize LnTPPCl(DMIE) complexes of the smaller lanthanides Er, Ho,

Tm, and Yb were used to try to make the complexes of the larger lanthanides,

neodymium (Nd) and praseodymium (Pr). After four hours of refluxing the LnC13 with

the TPP anion in dry toluene, the UV/Vis spectrum of the reaction mixture showed free

TPP with an absorbance peak at 415 nm and no evidence of metallated porphyrin. The

reaction was then refluxed for twelve hours with the same results and no isolation of

product.

Half-Sandwich Complexes

Inspired by the recent work of the Bianconi group,52 we attempted another

synthetic route to obtain Nd and Pr porphyrin compounds. Bianconi recently reported the

synthesis of neodymium tris(1-pyrazolyl)borate diiode (NdTpI2(THF)2), and we pursued









the displacement of the iodide ligands with TPP dianion as an alternative route to the

desired complexes, NdTPPTp and PrTPPTp.

H





KTp NI NI
NdCl3(THF)3 THF

rt, 12h THF--Nd-THF
Cl Cl

Figure 2.3: Synthesis of NdTpCl2(THF)2.

In an attempt to make the analogous chloride complex, NdTpCl2(THF)2,

NdCl3(THF)3 was treated with KTp (Figure 2.3). After stirring for twelve hours, the

resulting blue solution was filtered, the solvent removed under reduced pressure and the

product was extracted with methylene chloride. Layering the CH2C12 solution with

pentane gave an immediate blue precipitate, which had proton NMR shifts corresponding

to the Tp protons at -0.55 ppm, 7.64 ppm and 13.2 ppm. The proton NMR, however, was

significantly different from the proton NMR of the diiodide complex in that the Tp peaks

had different chemical shifts and there were no peaks associated with coordinated THF.

The Biaconi group reported52 the synthesis of ytterium Tp chloride and bromide

complexes, but only the iodide complex of neodymium. These results suggested that

perhaps the chloride ions were not large enough to satisfy the coordination sphere of

neodymium and the complex was not a half sandwich but perhaps a dimer or higher

aggregate. Attempts to obtain crystals of this compound were unsuccessful.









LnTPPI(DME) Complexes

Given the differences in the behavior of the chloride and iodide complexes, the

complexes Ndl3(TIF)4 (1) and Prl3(THF)4 (2) were prepared according to the literature

procedure used for Cel3(THF)4 as shown in equation 2.1.53

o THF
Ln + 3CH3CH2I THF LnI3(THF)n (2-1)

The lanthanide triiodide complexes 1 and 2 were used in salt metathesis reactions

with Li2TPP(DME)2 (Figure 2.4). After refluxing the lanthanide triiodide and TPP

dianion in toluene for four hours, the UV/Vis of the reaction mixture showed an

absorption at -425 nm corresponding to metallated TPP. The solution was then separated

from KI by hot filtration and after layering with pentane, the complexes NdTPPI(DME)

(3) and PrTPPI(DME) (4) precipitated in 74% and 72% yields, respectively.



I-Ln-O

S 2Li(DME)

N 8 N + Lnl3 Toluene 'N
reflux, 4h

N N




Ln Nd, Pr
Figure 2.4: Synthesis of 3 and 4.

In order to study the phosphorescence of TPP in our devices, we synthesized

gadolinium and lutetium porphyrin complexes whose metal centered excited states are

too high in energy to be sensitized by TPP. Similar to the previously stated procedure,

GdTPPC1(DME) (5) and LuTPPCl(DME) (6) were synthesized by reaction of the

lanthanide trichloride with the dilithiated TPP compound.









Single crystals of NdTPP(I)(THF)2 were grown by slow diffusion of pentane into a

saturated solution of THF and were analyzed by X-ray crystallography. The thermal

ellipsoid plot of the solid-state structure of the neodymium complex with selected atom

labels is shown in figure 2.5. The crystal structure shows that the lanthanide ion is seven

coordinate with the metal ion bonded to the four nitrogens of the porphyrin ring, one

iodide and two oxygens from coordinating THF molecules. The metal ion is too large to

fit into the porphyrin cavity and so the porphyrin ring adopts a domed conformation to

maximize the Ln-N interactions. The average Nd-N bond length is 2.436(1) A and the

Nd atom sits 1.286(6) A above the mean plane of the coordinating nitrogens on the

porphyrin ring.

Single crystals of LuTPPCl(DME) (6) suitable for X-ray structure determination

were grown from a saturated solution of CH2C2 layered with pentane. The thermal

ellipsoid plot of the solid-state structure of the lutetium complex with selected atom

labels is also shown in figure 2.4. Similar to the Nd complex, the LuTPPCl(DME)

complex is seven coordinate with the metal ion bonded to the four nitrogens of the

porphyrin ring, as well as one chloride ion and two oxygens from the coordinating DME

molecule. The ionic radius of the Lu ion is about 0.15 A smaller than the Nd ion, giving

rise to shorter averaged metal-ligand bond distances. The average Lu-N bond length is

2.306(1) A and the Lu ion sits 1.098(0) A above the mean plane defined by the nitrogen

atoms of the porphyrin ring.












1 -1
Ii>4


--wo


02 -


.--.-


Figure 2.5: Thermal ellipsoid plots of the molecular structure of NdTPPI(DME) (top) and
LuTPPCl(DME) (6) (bottom), showing selected atom labels, drawn at the 50
% probability level. The hydrogen atoms have been excluded for clarity.
LnTPP(L) Complexes
The LnTPPX(DME) compounds have been used to synthesize a series of sterically

saturated monoporphyrin lanthanide complexes via a second salt metathesis reaction,

replacing the halide and solvent molecule with a mutlidentate, monoanionic ancillary

ligand. The low-lying emissive levels of these lanthanide ions are easily quenched by

molecular vibrations, especially O-H and C-H oscillators.5456 In order to enhance the









luminescence properties of the complex, the ancillary ligand must provide enough steric

bulk to prevent quenching agents such as water from interacting with the metal.

Furthermore, the polydentate, monoanionic axial ligand saturates the coordination sphere

of the metal center while maintaining a neutral complex. The complexes that we have

used to fill the remaining coordination sites of the metal are hydrotris (pyrazolyl) borate

(Tp), (cyclopentadienyl)tris(diethylphosphinito)cobalt (K(LOEt)), and

(hydroxy)quinolate (Q) ligands.

LnTPP(Tp) complexes

Similar to cyclopentadienide ligands, Tp ligands are one of the most common

supporting ligands in transition metal and lanthanide chemistry,7 with the first

lanthanide-polypyrazolylborate complex published by Bagnall in the 1970s.58 The

binding of the monoanionic ligand occurs in a tridentate fashion with the nitrogens of the

pyrazolyl binding to the lanthanide. The binding properties of this ligand are easily tuned

by simple manipulation of the 3- and 5-substituents of the pyrazolyl rings. Synthesis of

LnTp complexes is a simple salt metathesis reaction involving a lanthanide halide or

triflate and the potassium or sodium salt of the ligand to give a mono-, bis-, or tris-ligand

complexes, depending on the steric bulk of the ligand.

The LnTPP(Tp) complexes of holmium, erbium, thulium and ytterbium were

synthesized previously by Foley.51'59 Recently Wong et al. published another synthetic

route for the NdTPP(Tp) complex, prepared by reaction of the Ln(Porphyrin)(H20) 3C1

with KTp.60 The analogous praseodymium, neodymium,59 gadolinium and lutetium

complexes were synthesized by reaction of the potassium salt of Tp (KTp) with

LnTPPX(DME) (where X = I for Pr and Nd and X = Cl for Gd and Lu) in DME giving

the desired LnTPPTp (Figure 2.6). The reaction was performed under an inert









atmosphere to prevent the hydrolysis of the LnTPP bonds. After stirring at room

temperature for twelve hours, the products were extracted with CH2C2 and were then

isolated as purple crystalline solids in high yields by recrystallization from a mixture of

CH2C2 and pentane. The purity of the bulk material was confirmed by elemental

analyses and the molecular structure of NdTPPTp (7) was determined by X-ray

crystallography.

H






XLO DME
X-Ln-O + KTp Ln
rt, 12h

Ph Ph Ph Ph


N N N N I

N -N
Ph Ph Ph Ph


Ln = Pr, Nd, Gd, Lu

Figure 2.6: Synthesis of LnTPP(Tp) where Ln = Pr, Nd, Gd, Lu.

Slow diffusion of pentane into a saturated CH2C2 solution gave X-ray diffraction

quality crystals of NdTPPTp (7) (Figure 2.7). The coordination geometry of the metal

ion is best described as a distorted capped trigonal prism with the trigonal prism being

composed of three of the porphyrin N atoms and the three pyrazolyl N atoms with the

capping group being the final porphyrin N atom. The distortion in the structure is due to

the different bond lengths between Nd and the nitrogens atoms of the porphyrin group.









The distances of Nd-N(4) and Nd-N(1), which are 2.458 A and 2.447 A respectively, are

slightly longer than the Nd bond between N(2) and N(3), which are 2.427 A and 2.421 A,

respectively. The center of the Nd atom is 1.302(4) A above the center of the mean plane

defined by the pyrrole nitrogens of the porphyrin and 1.891(7) A below the mean plane

defined by the pyrazolyl nitrogen plane. The pyrrole rings deviate from the mean plane

defined by the pyrrole nitrogens by 17.00, 8.90, 15.30 and 5.1 for the rings containing

N(1), N(2), N(3) and N(4) respectively. The porphyrin becomes puckered in order to

accommodate the large metal, causing these deviations from the mean plane.









I d
N4 ^








Figure 2.7: Thermal ellipsoid plot of NdTPPTp (7) showing selected atom labels drawn at
the 50 % probability level. The hydrogen atoms have been excluded for
clarity.

LnTPP(LOEt) complexes

The tripodal ligand [(CsHs)Co{P(O)(OEt)2}3] was first reported in 197461 by Klaui

and has been shown to be a versatile compound in the synthesis of heterobimetallic

complexes. Coordination occurs through the oxygen atoms to form a tridentate ligand

that has been demonstrated by Klaui et al. to form stable coordination compounds with









many metal ions including lanthanide ions.62 Edelmann et al. have recently reported the

first organolanthanide-LOEt complex by reaction of [(r8-CsHs)Sm(tC-C1)(THF)]2 with

Na(LOEt) to obtain (r8-CsHs)Sm(LOEt).63

The synthetic procedure for preparing LnTPP(LOEt) is similar to that used for the

TP complexes. The synthesis and crystal structure of the ErTPP(LOEt) and

YbTPP(LOEt) complexes have been reported by Wong et al. 64,65 This procedure,

however takes 48 hours and the desired products must be isolated and purified by column

chromatography. The procedure developed by our lab synthesizes the same product in a

one pot, 12 hour reaction in DME using simple recrystallization techniques to isolate

LnTPP(LOEt) (Ln= Ho, Er, Tm, Yb) in high yields.59 The LOEt complexes of Nd and

Pr were synthesized using THF as the solvent. The reaction of K(LOEt) and

NdTPPI(DME) in DME led to low yields, with the proton NMR spectrum showing free

ligand (Figure 2.8).


EtO \OEt




0 0
I-Ln-O _+ K(LOEt) THF Ln
rt, 12h

Ph N Ph Ph N Ph


N N N N

/ 2 N
Ph \ Ph Ph Ph

Figure 2.8: Synthesis of LnTPP(LOEt), where Ln = Nd (11), Pr (12).









LnTPP(quinolate) complexes

Whether used as an emitting layer or an electron transport layer, tris-(8-

hydroxyquinoline)aluminum (AlQ3) is one of the most frequently used materials for

organic light emitting devices.66,67 The incorporation of this known electron transporter

into blends of our lanthanide porphyrin complexes resulted in a significant increase in

device efficiency.38 AlQ3 likely increases the electron transport properties of the

material, thereby improving the charge carrier balance in the devices. Inspired by this

work, we synthesized a lanthanide porphyrin complex with quinolate capping ligands

The procedure for the synthesis of the YbTPP(Q)THF (13) complex was analogous

to the TP and LOEt procedures. The potassium salt of quinlone (KQ) was added to

YbTPPC1(DME) in THF under an inert atmosphere for twelve hours to give the desired

product (Figure 2.9).





0 C
Cl-Yb-0 + KQ THF O
rt, 12h

Ph Ph Ph Ph


N N N N


Ph N~ Ph Ph Y NPh


Figure 2.9: Synthesis of YbTPP(Q)THF (13).

Crystals suitable for X-ray diffraction were grown from THF solutions of the

complex layered with pentane. The crystal structure of 13 (figure 2.10) illustrates that the









complex is a monomer with a coordination number of seven around the metal center.

The ytterbium sits 1.102(5) A above the plane of the porphyrin and has an average Yb-N

bond distance of 2.331(3) A. The bond distances on the ligand are 2.180(2) A and

2.538(3) A for Yb-O(1) and Yb-N(5), respectively. The quinolate ligand is not bulky

enough to shield the lanthanide from solvent coordination as seen by the coordinating

THF molecule with a bond distance of 2.397(3) A for Yb-O(2).





















Figure 2. 10: Thermal ellipsoid plot of YbTPP(Q)Tf (13) showing selected atom labels
-


I.- ...-.r
-/-



1^ '






Figure 2.10: Thermal ellipsoid plot ofYbTPP(Q)THF (13) showing selected atom labels
drawn at the 50 % probability level. The hydrogen atoms have been excluded
for clarity.

NMR Studies

In this section, the proton 1-D and 2-D NMR spectroscopy results will be

discussed. Despite their paramagnetic nature, lanthanide complexes can give NMR

spectra having narrow line widths with large spectral windows due to the nature of the f-

electron paramagnetism.43'68 The paramagnetic shifts are dependent on the electronic

structure of the lanthanide ion as well as the position of the resonating nuclei with respect









to the metal. Because of the uncertainty of the paramagnetic shifts of these new

compounds, the proton peaks cannot be assigned as easily as in diamagnetic materials.

However, the use of the relative integrals as well as simple 2-D NMR experiments has

allowed us to do a complete assignment of the proton NMR spectra of these compounds.

NdTPPTp

The 1-D proton NMR spectrum of 7 is shown in figure 2.11. Assuming the rotation

of the phenyl rings on the porphyrin is slow compared to the time scale of the

experiment,68'69 there should be nine proton peaks. Of these nine peaks, five of the peaks

correspond to the protons from the phenyl rings and have an integration of four, three of

the peaks correspond to the Tp protons and have an integration of three and the ninth

peak corresponds to the pyrrole protons and has an integration of eight. (The B-H proton

of the Tp group is almost never observed, even in diamagnetic compounds, due to

quadrapolar broadening from the boron atom). The spectrum, however, only shows eight

peaks with integrated ratios (labeled A-H) of 3:4:8:7:4:4:3. Studies have shown that

paramagnetic complexes have a significant temperature dependence of their resonance

shifts.43 Lauffer et al. showed that with lanthanide complexes of

diethylenetriaminepentaacetate, overlapping singlets at room temperature can be

observed at low temperatures.70 Variable temperature NMR studies (Figure 2.12) in the

range of 200 to 500 C show that peak D splits into two peaks, Da and Db, with relative

integration of 4 and 3 respectively. Using the integrals, peaks A, Db and H are assigned

to the Tp protons while peaks B, Da, E, F and G are assigned to the protons on the phenyl

ring and peak C is assigned to the protons on the pyrrole.













N )Db

\I/ H
Nd

Ph NPh


N N
G I
F Ph

C
E B
Da

C Da

Db
A E
jF H


14 12 10 0 6 4 2 0 -2 -4 -6 ppi



Figure 2.11: H NMR of NdTPPTp (7).

By running a COSY NMR experiment, we were able to observe the proton

couplings that are obscured by the line width in the 1-D NMR spectrum. By looking at

the reference peaks along the horizontal or vertical axes and their cross peaks off the

diagonal, the proton-proton correlations are seen and used in peak assignment. The 2-D

spectra of 7 (figure 2.13) show a cross peak between peaks A and Db with no other

couplings, confirming the Tp assignment of these two protons.












S509 C


Da A Db 400C



S30P C


D E
200 C


,0 6.9 6. 6.7 6,6 6.5 6,4 p


Figure 2.12: Variable temperature NMR of the phenyl region of NdTPPTp (7) from 20-
50.

Because of its proximity to the paramagnetic nucleus the relaxation time of peak H

is too fast to allow the appearance of the crosspeaks between H and either Db or A in the

NMR spectrum. So, peak H is assigned the proton nearest the metal because it is shifted

significantly upfield and, with a half width of 22.4 Hz, it is the broadest Tp peak. The

expanded area of the COSY spectrum (figure 2.13) shows correlations between peaks B

and Da, Da and E, E and F, and F and G. Because of their correlations with only peaks Da

and F respectively, peaks B and G are assigned the ortho protons on the phenyl ring. The

half width of peak G is 15.6 Hz while the half width of peak B is 15.0 Hz, so G is

assigned to the proton pointing towards the metal and Tp. The rest of the assignments

were made using the same logic, with peak F being the meta proton pointing towards the

metal and Da pointing away and E being the para proton.














F2
(ppnm







-4
-2

0-




4-

6-




10-

12-:

14

i c-


14 12 10 8


F2



5.5

6.

6.5

7.0

7.5

8.0-

8.5


L-.
-'.9.


FD


Db


- A-Db


l "'l"" 11" 1 1" 111"1" 1 "l""I "" "111 ""l""II' l "I'
6 4 2 0 -2 -4 -6

F1 (ppm)


Da-E
Da-E


9,5 8.0 7.5 7.0 6.5 6.0 5.5

FL (pPM)


Figure 2.13: Full COSY NMR of NdTPPTp (7) (top), expansion from 8.5-5.5 ppm
(bottom).


"'


II


I


9.0


0-, do









NdTPP(LOEt)

One and two-dimensional NMR experiments were used to analyze the LOEt

complexes as well. The 1-D proton NMR spectrum (figure 2.14) shows nine peaks for

NdTPP(LOEt) (11). Similar to the analysis of 7, the peaks can be assigned to protons via

their relative integration. Starting with peak A at 10.16 ppm, the integrated ratios are

5:4:8:4:4:4:12:18. There is one peak with an integration of 5, which is expected for the

Cp protons, two peaks with integration of 12 and 18,which are the methylene and methyl

protons on the LOEt ligand respectively, and then there are the expected number of peaks

and integration for the phenyl and pyrrole protons. The COSY spectra ofNdTPP(LOEt)

(11) (figures 2.15 and 2.16) show that peaks H and I are coupled to each other,

supporting the ethoxy group assignment. While not observed in the 1-D NMR, the 2-D

NMR spectrum shows the inequivalence of the diastereotopic protons on the methylene

group. Looking at the expanded region, the cross peaks show that peaks B and G are the

ortho protons, C and F are the meta protons and peak E is the para proton. Because peak

G is broader than peak B, it is assigned the ortho proton closest to neodymium. The half

widths of G and B were 25.3 Hz and 24.1 Hz, respectively.





































D


A





AA
a c 1 F U


SI Il l II I 9 II 4 3 1 pp
10 9 8 7 6 5 4 3 2 1 -0 ppm


Figure 2.14: 'H NMR spectrum of NdTPP(LOEt) (11).













F2
(ppm]

-(0-


11---
10 9 8 7 6 5 4 3 2 1 -0 -1

Fl (ppm)
Figure 2.15: COSY NMR of NdTPP(LOEt) (11).


G






F

+D E F-G
.. E-F

** C i C-E



B B-C

' I I I I I I I I I I I I I I I '
8 7 6 5 4 3 2

F1 (ppm)


Figure 2.16: COSY NMR of NdTPP(LOEt) (11), expansion from 8-2ppm.


I0
SH H-l



G




SF

E

C
B


F2
(ppm









LnTPP(L) Photoluminescence and Electroluminescene Studies

After the syntheses and full characterization of the LnTPP(L) complexes, the

photoluminescence (PL) and electroluminescence (EL) properties of these compounds

were examined. Recent work39 has shown that formulation of the EL device materials

can be guided by PL studies. Due to the lengthy process of device construction, PL

studies were carried out on blends of polymer and the lanthanide complexes to determine

if the complexes would be luminescent. PL studies on NdTPPTp, performed by Ben

Harrison, showed NIR emission around 900 nm, 1069 nm and 1300 nm, which are the

4F3/2-> 419/2, 411/2, and 4113/2 transitions ofNd (figure 2.17). The quantum efficiency (0em)

was determined to be 2.4 %.59 PL studies ofNdTPP(LOEt) had similar results (figure

2.17).59 Reported quantum efficiencies of other Nd-complexes range from 0.4 %71 to

1.0 %.72









C

-J
I



900 1000 1100 1200 1300 1400 1500
Wavelength I nm


Figure 2.17: PL emission NdTPPL (solid lines, L = Tp, dashed lines, L = LOEt).

PL studies of the Pr complexes showed no NIR luminescence and therefore no

devices were made with these complexes. Lack of emission is not surprising in that the










energy states that are below the 37-7* of the TPP ligand are closely spaced (separations of

2000-4000 cm-1), causing nonradiative decay to be efficient.59

The device construction is shown in figure 2.18. The hole transport layer, PEDOT-

PSS, was spin coated onto ITO covered glass, followed by the active layer (consisting of

the lanthanide complex blended with polystyrene (PS)) and then finally the calcium layer

as well as a layer of aluminum to prevent oxidation of the calcium.

While most of the device construction used the conjugated polymer, PPP-OR11,73

our labs have demonstrated the fabrication of NIR-LEDs using blends of our lanthanide

porphyrin complexes in non-conjugated host polymers, where the porphyrin serves as not

only the charge carrier but also luminescent material (figure 2.19).73,74




Aluminum
Passivation Layer
(150-200 nm)
Calcium Electrode
(electron injection layer)
(-5nm)
Active Layer (-50-100 nm)
Host:
PEDOT-PSS PS
Dopant:
Hole Transport Layer Dopant:
(-50 nm) Ln Complex


ITO Electrode NIR Transmissive
(hole injection) Substrate


Figure 2.18: Device architecture.



































Figure 2.19: Charge hopping cartoon.

Devices made with blends of NdTPP(LOEt) and PS (2:1 weight ratio,

complex:polymer) turned on at about 4 V and were able to operate efficiently at 9 V,

producing NIR emission around 900 nm, 1069 nm and 1300 nm, which are the 4F3/2-

419/2, 4111/2, and 4113/2 transitions of Nd (figure 2.20).74



1.0 -
II
"' III,
S0 8

0 I 6
"U I ':

U) I "
S04 -



oo \ i :
II' 1
Z 02


800 900 1000 1100 1200 1300 1400 1500 1600
Wavelength / nm
Figure 2.20: Electroluminescence emission of Ln(TPP)(LOEt) in polystyrene measured at
9 V. Ln = Nd (solid line), Yb (dashed line) and Er (dotted line).74









The quantum efficiency of blends with YbTPPTP, polystyrene and the known

electron transporter, 8-hydroxyquinoline aluminum (AlQ3) is ten times higher than

devices without AlQ3. Through these studies, we have found that LnTPP(L) is more

efficient in the transport of holes and, therefore, creates a charge imbalance and low

device efficiencies. There have been many studies on the poor ability of lanthanides to

transport charge carriers, especially electrons.21,75,76 With hopes of improved charge

balance, PL and EL studies of YbTPP(Q)THF (13) were conducted by Garry

Cunningham. PL studies showed NIR emission with a predominant peak 980 nm. The

quantum efficiency was calculated to be 0.0091 in CH2C12, which is significantly lower

than efficiencies found for our other YbTPPL complexes.59 Devices made with 13

emitted -970 nm with a quantum efficiency of 0.00002-0.00004, depending on device

loading of the complex. Again, these efficiencies are found to be lower than efficiencies

previously reported for YbTPPL complexes.73 As seen in the crystal structure of 13, the

capping ligand does not complete the coordination sphere of Yb and is not sterically

hindering enough to prevent solvents, such as THF, from coordinating to the complex. It

is likely that the proximity of the C-H bonds in the coordinated THF molecules provides

efficient pathways for nonradiative decay, thus lowering the quantum efficiency of the

complex.

Summary and Conclusions

In summary, novel neodymium and praseodymium complexes of

tetraphenylporphyrin have been synthesized, thus completing the series of NIR emitting

lanthanide porphyrin complexes. Through a simple salt metathesis reaction with the

corresponding triiodides and dilithioTPP complexes, LnTPPI(DIME) of Nd and Pr

complexes were cleanly isolated in good yields. Analogous compounds of gadolinium









and lutetium were synthesized in the same fashion. From these starting materials, the

lanthanide compounds were easily completed with a number of ancillary ligands

including Tp, LOEt and quinolate. These compounds have been fully characterized

through crystallography, proton and COSY NMR studies, with proton peak assignment

accomplished by integration of the 1-D proton spectrum and from proton correlations

observed in the 2-D spectrum.

Recent work has demonstrated that devices do not require conjugated polymers and

that blends of the lanthanide complexes with nonconjugated polymers produce NIR

emission. PL studies found that devices blended with Nd complexes give NIR emission

with a quantum efficiency of about 0.0024, while Pr complexes do not emit in the NIR.

The NdTPPL complexes produce NIR emission with quantum efficiencies higher than

published reports, supporting the design of emitting Ln complex consisting of the

porphyrin sensitizing molecule and ancillary capping ligand.

PL and EL studies carried out with blends of NdTPP(L) and PS show that the TPP

complex acts as the charge carrier that is more efficient in hole transport. Synthesis of

the YbTPPQ was an attempt to balance the charge transfer in the emissive layer.

However, the capping ligand is not sterically encumbering enough to hinder solvent

coordination, facilitating nonradiative decay pathways and lowering device efficiency.

Experimental

Materials and Reagents

Unless otherwise stated, all syntheses were carried out on a double manifold

Schlenk line under an atmosphere of nitrogen or in a N2 filled glovebox. Glassware was

oven dried prior to use. Methylene chloride, dimethoxyethane, chloroform and

dimethlyforamide were purchased from Fisher Scientific and were dried with an









appropriate drying agent.77 Pentane, tetrahydrofuran and toluene were purchased from

Aldrich Chemicals and dried by passing through a column of activated alumina.

Following dehydration, all solvents were degassed and stored over 4 A molecular sieves

in resealable ampoules with fitted Teflon valves. 8-hydroxyquinoline was purchased

from Aldrich and used as received. The complexes

(Cyclopentadienyl)tris(diethylphospinito)cobalt(I) (LOEt),78 hydridotris(1-

pyrazolyl)borate (TpH),79 TPNdCl2THF,52 (LOEt)NdCl2THF,52 TPP,s Li2TPP,8 and

YbTPPC1(DME)51 were synthesized following literature procedures. Potassium 8-

hydroxyquinoline (KQ) was synthesized by reacting 8-hydroxyquinoline with potassium

hydride in THF. Elemental analyses were performed at the University of California,

Berkley, Micro-Mass Facility or University of Florida Spectroscopic Services. Proton

NMR spectra were measured at 300 MHz at room temperature, unless otherwise stated

and on Varian Gemini 300, VXR 300, Mercury 300 or Bruker 300 NMR machines.

Chemical shifts were referenced to residual solvent peaks and are reported relative

tetramethylsilane. The spectral window was also different for each metal complex and

was determined by expanding the window until peak positions remained unchanged.

COSY spectra were run using the standard parameters of the instrument. All UV/VIS

spectra were run in 1 cm path length quartz cuvettes in CH3CI unless stated otherwise.

The samples were prepared and run under N2 on a double-beam Cary-100 UV-visible

spectrometer.

Synthesis

Ndl3(THF)4 (1)

In a round bottom flask equipped with a side arm, Nd metal (4.98 g, 0.0346 mol)

was washed with dry THF (3 x 30 mL). Dried and degassed ethyliodide (22 ml, 0.27









mol) was then added along with 30 mL of THF. After refluxing under N2 for 20 hours,

the brown solution was cooled and the THF removed in vacuo. Soxhelt extraction of the

brown solid was performed in ca. 100 mL of THF under N2 for 3 days. Following the

completion of the extraction, the THF was removed, giving 1 as a blue solid in 46% yield

(13 g, 0.016 mol).

PrI3(THF)4 (2)

Using the same procedure for 1, Pr metal (2.97 g, 0.0211 mol) and CH3CH2I (13.1

ml, 0.169 mol) were refluxed under N2 in dry THF (30 mL) giving 2 as yellow solid in

38% yield (6.1 g, 0.0075 mol).

NdTPPI(DME) (3)

NdI3(THF)4 (0.51 g, .61 mmol) and Li2TPP(DME) (0.499 g, 0.615 mmol) were

added together in the dry box. About 40 mL of dry toluene was then added and the

purple solution was refluxed under N2. The reaction was followed by UV/VIS

spectrometry (a peak at 425 nm with no peaks at -415 nm indicated completion). After

refluxing for four hours, the solution was filtered while hot via cannula. The residue was

then washed with CH3Cl (2 x 20 mL) and the toluene and CH3C1 solutions were

combined and reduced in volume to 10 mL. The solution was then layered with ca. 20

mL of pentane. After 12 hours, the solution was filtered, leaving a red/purple solid

(0.443 g, 0.455 mmol) in 74% yield. 1H NMR (300 MHz, CD2C12): 6 8.95(vl/2 = 5.78

Hz, 8H, H-pyrrole), 8.12(vl/2= 17.33 Hz, 4H, o-C6H5 TPP), 7.56 (vi/2= 19.32 Hz, 4H, m-

C6H5 TPP), 7.31 (vl/2= 5.71 Hz, 4H, p-C6H5 TPP), 6.92 (vl/2= 19.49 Hz, 4H, m-C6H5

TPP) 4.90 (v/2 = 18.72 Hz, 4H, o-C6H5 TPP), -5.42 (vl/2 = 217 Hz, 10H, DME). UV/VIS

(CH2C12) )hax (log E): 422 (5.45), 514(3.95), 552(4.37), 590(3.95) nm. Anal. Calcd. for

C48H38N4NdIO2: C, 59.19; H, 3.93; N, 5.75. Found: C, 57.31; H, 4.02, N, 5.52.









PrTPPI(DME) (4)

In the same fashion as 3, PrTPPI(DME) was synthesized by refluxing Prl3(THF)4

(0.5 g, 0.1 mmol) and Li2TPP (0.501 g, 0.108 mmol) in ca. 30 mL of toluene for four

hours. The purple solid was isolated in 74% yield (0.44g, .451mmol). H NMR (300

MHz, CDC13): (7.73 (vl/2 = 16.19 Hz, 4H, o-C6H5 TPP)), 6.81(v1/2= 18.66 Hz, 4H, m-

C6H5 TPP), 6.29 (v/2 = 5.07 Hz, 4H, p-C6H5 TPP,), 5.53 (v/2 = 5.7 Hz, 8H, H-pyrrole),

5.33(v/2 = 18.79 Hz, 4H, m-C6HS TPP) 0.78 (v/2 = 17.79 Hz, 4H, o-C6H5 TPP). UV/VIS

(CH2C12) )max (log E): 424 (5.45), 514(3.95), 552(4.37), 590(3.95) nm. Anal. Calcd. for

C48H38N4PrIO2: C, 59.39; H, 3.92; N, 5.77. Found: C, 58.99; H, 3.96; N,5.84.

GdTPP(CI)DME (5)

In the glove box, Li2TPP(DME) (0.75 g, 0.80 mmol) and GdC13 (0.22 g, 0.80

mmol) were added to a Schlenk flask. Dry toluene (ca. 30ml) was then added and the

green/blue solution was refluxed under N2 for 3 hours, over time the color changed to

red. After refluxing, the solution was removed in vacuo and the compound extracted

with CHC13 (3 x 30 mL). The chloroform solution was reduced to ca. 20 mL and then

layered with hexane (30 mL) to give purple crystalline material in 55% yield (0.4 g, 0.5

mmol). UV/VIS (CH2C2) )max (log E): 425(5.46), 514(4.47), 552(4.87) nm. Anal. Calc.

for C48H38N4GdC102: C, 64.23; H, 4.25; N, 6.25. Found: C,65.06; H, 4.12; N, 6.12.

LuTPP(CI)DME (6)

In the same fashion of 5, LuTPPCl(DME) was synthesized by refluxing LuC13

(0.51 g, 1.7 mmol) and Li2TPP(DME) (1.58 g, 1.77 mmol) in ca. 30 mL of toluene for 3

hours. After the color change of the solution from green/blue to red, the solution was

removed in vacuo and the compound was extracted with CH2C12 (3 x 30 mL) and filtered.

The CH2C12 solution was reduced in volume to ca. 20 mL and then layered with hexane









(30 mL) to give purple crystalline material in 63% yield (0.99 g, 1.09 mmol). 1H NMR

(C6D6): 59.09(s, 8H), 8.47(m, 4H), 8.07(m, 4H), 7.57(m, 12H). UV/VIS (CH2C12) max

(log E): 420(4.80), 510(3.75), 548(3.961), 585(3.57) nm. Anal. Calc. for

C48H38N4LuC102: C, 63.13; H, 4.16; N, 6.14. Found: C, 59.49; H, 3.78; N, 5.71.

NdTPPTp (7)

To a solution of 3 (0.15 g, 0.15 mmol) in dry DME (30 mL), was added KTP

(0.041 g, 0.15 mmol). The reaction mixture was left to stir for twelve hours at room

temperature. The solution was removed in vacuo and the purple compound was extracted

with ca. 30 mL of CH2C12, leaving a white residue of KI. The volume of the red/purple

solution was reduced to 10 mL and then layered with pentane (10 mL). After being

cooled to -100 C for 12 hours, the solution was filtered, leaving a purple solid. The

mother liquor was reduced in volume (ca. 10 mL) to allow more product to precipitate.

Recrystallization of the combined solids from CH2Cl2/pentane gave X-ray quality crystals

in 64% yield (0.093 g, 0.096 mmol). 1H NMR (C6D6): 3 14.65(v1/2 = 5.61 Hz, 3H, H-

Tp), 7.97(v1/2 = 15.05 Hz, 4H, o-C6H5 Tpp), 7.82(vl/2 = 4.25 Hz, 8H, H-pyrrole),

6.93(v1/2 = 5.08 Hz, 7H, m-C6H5 Tpp, H-Tp), 6.47(vi/2 = 3.25 Hz, 4H, p-C6H5 Tpp),

5.75(v1/2 = 16.88 Hz, 4H, m-C6H5 Tpp), 2.88(v1/2 = 15.66 Hz, 4H, o-C6H5 Tpp), -

6.23(vl/2 = 22.41 Hz, 3H, H-Tp). UV/VIS (CH3C1), ax (log E) = 425(5.29), 555(4.36)

nm. Anal Calc. for C53H38BN10Nd: C, 65.76; H, 3.93; N, 14.47. Found: C, 65.67; H,

3.96; N, 14.33.

PrTPPTp (8)

Following the same procedure for 7, 4 (0.150 g, 0.155 mmol) and KTP (0.041 g,

0.15 mmol) were stirred together in dry DME (30 mL) for twelve hours at room









temperature. After recrystallization from CH2Cl2/pentane, 49% (0.073 g, 0.076 mmol) of

product was collected. H NMR (C6D6): 818.08(v1/2 = 4.89 Hz, 3H, H-Tp), 8.13(v1/2

14.81 Hz, 4H, o-C6H5 Tpp), 6.63(vl/2 = 5.09 Hz, 7H, m-C6HS Tpp, H-Tp), 5.90(v1/2 =

3.97 Hz, 4H, p-C6H5 Tpp), 5.36(v1/2 = 3.69 Hz, 8H, H-pyrrole), 4.64(v1/2 = 17.51 Hz,

4H, m-C6HS Tpp), -0.47(v1/2 = 14.09 Hz, 4H, o-C6H5 Tpp), -13.87(vl/2 = 11.23 Hz, 3H,

H-Tp). UV/VIS (CH3C1), max (log E) = 424(5.30), 516(3.78), 555(4.34), 592(3.84) nm.

Anal. Calc. for C53H38BN10Pr: C, 65.86; H, 3.93; N, 14.50. Found: C, 66.30; H, 3.91; N,

14.23.

GdTPPTp (9)

Following the procedure used to synthesize NdTPPTp, KTp (0.067 g, 0.26 mmol)

was added to a solution of GdTPPC1(DME) (0.24 g, 0.26 mmol) in toluene (ca. 20 mL).

The reaction was stirred overnight at room temperature. The purple solution was

removed in vacuo and the crude material was extracted with CH2C12 (ca. 30 mL). The

solution was filtered and layered with pentane (ca. 30 mL) to give the product in 55%

yield (0.14 g, 0.14 mmol). UV/VIS (CH2C12), max (log E) = 424(5.72), 513(4.33),

552(4.57), 590(4.33) nm. Anal. Calc. for C53H38BN10Gd: C, 64.76; H, 3.86; N, 14.25.

Found: C, 64.63; H, 3.71; N, 12.99.

LuTPPTp (10)

In the same manner as GdTPPTp, LuTPPCl(DME) (0.1 g, 0.10 mmol) and KTP

(0.027 g, 0.109 mmol) were mixed in toluene for twelve hours. After recrystalization

from CH2Cl2/pentane, 60% (0.059g, 0.06mmol) yield was recovered. 1H NMR (C6D6):

68.98(s, 8H), 8.29(m, 4H), 7.79(m, 4H), 7.43(m, 12H), 6.38(s, 4H), 6 =5.53(s, 3H),

5.25(s, 3H). UV/VIS (CH2C12), max (log ) = 421(5.12), 513(4.67), 550(4.93), 588(4.66)









nm. Anal. Calc. for C53H38BN10Lu: C, 63.61; H, 3.80; N, 14.00. Found: C, 63.43; H,

3.51; N, 13.91.

NdTPP(LOEt) (11)

To a stirring solution of 3 (0.125 g, 0.128 mmol) in dry THF (30 mL) was added

K(LOEt) (0.075 g, 0.125 mmol). The purple solution was stirred for twelve hours at

room temperature. The solvent was then removed in vacuo and the product was extracted

into 30 mL of toluene. The volume of toluene was reduced to about 10 mL and layered

with ca. 10 mL of pentane. After 24 hours at -780C, the purple precipitate was isolated

by filtration and recrystallized from CH2C2/pentane. The crystals were washed with

pentane (3 x 10 mL) to give 11 in 30% yield (0.05 g, 0.04 mmol). 1H NMR(C6D6): 6

10.13(v1/2 = 3.28 Hz, 5H, H-Cp), 7.98(v1/2 = 19.35 Hz, 4H, o-C6H5 Tpp), 6.80(vi/2 =

20.88 Hz, 4H, m-C6H5 Tpp), 6.53(v1/2 = 4.32 Hz, 8H, H-pyrrole), 6.35(v1/2 = 3.22 Hz,

4H, p-C6H5 Tpp), 5.61(v1/2 = 20.32 Hz, 4H, m-C6H5 Tpp), 2.02(v1/2 = 20.63 Hz, 4H, o-

C6H5 Tpp), -0.26(v1/2 = 47.23 Hz, 12H, -OCH2CH3), -0.83(v1/2 = 11.27, 18H,

OCH2CH3). UV/VIS (CH3CI), Xax (log ) = 427(5.42), 518(3.93), 560(4.30), 599(3.97)

nm. Anal. Calc. for C61H63CoN409P3Nd: C, 56.83; H, 4.69; N, 4.35. Found: C, 55.13;

H, 4.81; N, 3.90.

PrTPP(LOEt) (12)

The same procedure as 11 was used. PrTPPI(DME) (0.2 g, 0.2 mmol) and K(LOEt)

(0.121 g, 0.206 mmol) were reacted to give 12 in 30% yield (0.08g, 0.062mmol). H

NMR (C6D6): 314.92(v1/2 = 1.79 Hz, 5H, H-Cp), 7.96(v1/2 = 23.50 Hz, 4H, o-C6H5 Tpp),

6.28(v1/2 = 26.26 Hz, 4H, m-C6Hs Tpp), 5.45(v1/2 = 3.21 Hz, 4H, p-C6H5 Tpp), 3.96(vi/2

= 26.20 Hz, 4H, m-C6H5 Tpp), 3.04(v1/2 = 2.47 Hz, 8H, H-pyrrole), -2.16(v1/2 = 13.98









Hz, 18H,-OCH2CH3), -2.39(v1/2 = 30.25 Hz, 6H, -OCH2CH3), -2.59(v1/2 = 27.79 Hz, 6H,

-OCH2CH3), -3.02(v1/2 = 25.20 Hz, 4H, o-C6H5 Tpp). UV/VIS (CH3CI), Xmax (log E) =

425(5.14), 520(3.90), 559(4.35), 600(4.03) nm. Anal Calc. for C61H63CoN409P3Pr: C,

56.93; H, 4.78; N, 4.33. Found: C, 55.73; H, 4.96; N, 3.84.

YbTppQ(THF) (13)

In the glove box, K(8-hydroxyquinolate) (KQ) (0.02 g, 0.01 mmol) was added to a

solution of YbTPPC1(DME) (0.1 g, 0.01 mmol) in THF (30 mL) and stirred for 12 hours.

The solvent was removed under reduced pressure and the resultant solid was extracted

with CH2C12 (3 x 30 mL). The solution was reduced to ca. 10 mL and layered with ca.

20 mL of pentane, giving 13 as a purple crystalline solid (0.08 g, 57%). Crystals suitable

for single crystal X-ray diffraction studies were grown from a saturated solution of THF

(10 mL) that was layered with pentane (20 mL). UV/VIS (CH2C12) Xmax (log E): 422

(5.43), 512 (3.93), 552 (4.26), 589 (3.95) nm. Anal. Calc. for C57H42N502Yb: C, 68.21;

H, 4.19; N, 6.90. Found: C, 67.48; H, 4.45; N, 6.97.

X-ray

NdTPPI(THF)2

Data were collected at 173 K on a Siemens SMART PLATFORM equipped with A

CCD area detector and a graphite monochromator utilizing MoKa radiation (X = 0.71073

A). Cell parameters were refined using up to 8192 reflections. A full sphere of data

(1850 frames) was collected using the co-scan method (0.30 frame width). The first 50

frames were remeasured at the end of data collection to monitor instrument and crystal

stability (maximum correction on I was < 1 %). Absorption corrections by integration

were applied based on measured indexed crystal faces.









The structure was solved by the Direct Methods in SHELXTL5, and refined using

full-matrix least squares. The non-H atoms were treated anisotropically, whereas the

hydrogen atoms were calculated in ideal positions and were riding on their respective

carbon atoms. The asymmetric unit consists on the complex and a disordered thf

molecule. The THF molecule could not be modeled properly, thus program SQUEEZE, a

part of the PLATON package of crystallographic software, was used to calculate the

solvent disorder area and remove its contribution to the overall intensity data. The

complex has its iodine and two THF ligands disordered about a 2-fold rotation axis

perpendicular to the plane of the macrocycle but only the Iodine atom of the minor part

could be seen due to its small site occupation factor (refined to 5% then fixed in the final

cycles of refinement). A total of 548 parameters were refined in the final cycle of

refinement using 21110 reflections with I > 2o(I) to yield R1 and wR2 of 4.06% and

10.31%, respectively. Refinement was done using F2

LuTPPCI(DME)

The crystal was mounted in a nylon cryoloop from Paratone-N oil under argon gas

flow. The data were collected on a Bruker SMART APEX II charge-coupled-device

(CCD) diffractometer, with KRYO-FLEX liquid nitrogen vapor cooling device. The

instrument was equipped with graphite monochromatized MoKac X-ray source (k=

0.71073 A), with MonoCap X-ray source optics. A hemisphere of data was collected

using co scans, with 5-second frame exposures and 0.3 frame widths. Data collection

and initial indexing and cell refinement were handled using APEX II software. Frame

integration, including Lorentz-polarization corrections, and final cell parameter

calculations were carried out using SAINT+ software. The data were corrected for









absorption using the SADABS program. Decay of reflection intensity was monitored via

analysis of redundant frames. The structure was solved using Direct methods and

difference Fourier techniques. All hydrogen atom positions were idealized, and rode on

the atom they were attached to. The final refinement included anisotropic temperature

factors on all non-hydrogen atoms. Structure solution, refinement, graphics, and creation

of publication materials were performed using SHELXTL.

NdTPPTP

Data were collected at 173 K on a Siemens SMART PLATFORM equipped with A

CCD area detector and a graphite monochromator utilizing MoKa radiation (k = 0.71073

A). Cell parameters were refined using up to 8192 reflections. A full sphere of data

(1381 frames) was collected using the co-scan method (0.30 frame width). The first 50

frames were remeasured at the end of data collection to monitor instrument and crystal

stability (maximum correction on I was < 1 %). Absorption corrections by integration

were applied based on measured indexed crystal faces. The structure was solved by

Direct Methods in SHELXTL5, and refined using full-matrix least squares. The non-H

atoms were treated anisotropically, whereas the hydrogen atoms were calculated in ideal

positions and were riding on their respective carbon atoms. The asymmetric unit consists

of two complexes and a pentane molecule disordered over a center of inversion. The

disorder is resolved where only the methyl groups are disordered. A total of 1208

parameters were refined in the final cycle of refinement using 12451 reflections with I >

2o(I) to yield R1 and wR2 of 3.69% and 6.42%, respectively. Refinement was done using

F2
F.









YbTppQ(THF)

Data were collected at 173 K on a Siemens SMART PLATFORM equipped with A

CCD area detector and a graphite monochromator utilizing MoKa radiation (k = 0.71073

A). Cell parameters were refined using up to 8192 reflections. A full sphere of data

(1850 frames) was collected using the co-scan method (0.30 frame width). The first 50

frames were remeasured at the end of data collection to monitor instrument and crystal

stability (maximum correction on I was < 1 %). Absorption corrections by integration

were applied based on measured indexed crystal faces.

The structure was solved by the Direct Methods in SHELXTL5, and refined using

full-matrix least squares. The non-H atoms were treated anisotropically, whereas the

hydrogen atoms were calculated in ideal positions and were riding on their respective

carbon atoms. Atoms C56 and C57 of the coordinated thfwere disordered and were

refined isotropically in two parts, second part being C56' and C57'. The asymmetric unit

consists of the complex, an uncoordinated thf and a pentane molecule. The THF and

pentane molecules were disordered and could not be modeled properly, thus program

SQUEEZE, a part of the PLATON package of crystallographic software, was used to

calculate the solvent disorder area and remove its contribution to the overall intensity

data. A total of 585 parameters were refined in the final cycle of refinement using 24756

reflections with I > 2o(I) to yield R1 and wR2 of 3.98% and 9.20%, respectively.

Refinement was done using F














CHAPTER 3
LANTHANIDE SUBSTITUTED TETRA(ARYL)PORPHYRIN AND
PHTHALOCYANINE COMPLEXES : SYNTHESIS, CHARACTERIZATION AND
LUMINESCENCE STUDIES

We have demonstrated that devices produce NIR emission when made with blends

of the lanthanide porphyrin complexes in non-conjugated host polymers such as

polystyrene. In these devices the porphyrin complex must serve as the charge carrier.

These studies have also demonstrated that LnTPP is more efficient in the transport of

holes and, therefore, creates a charge imbalance in the active layer of the device. This

imbalance leads to charge recombination outside the active layer and thus low device

efficiencies. In order to enhance device performance, we must enhance the charge

balance in our active layer by enhancing the electron transport. In this chapter, the

synthesis and characterization of substituted lanthanide-porphyrin and phthalocyanine

complexes will be discussed as will the effect of the substituents on device efficiency.

Substituted Tetra(aryl)porphyrins

Much work has been done with studying the substituent effects on the redox

properties of substituted tetraphenylporphyrins.82'83 These studies found that electron-

withdrawing and electron-donating groups affect the reduction and oxidation potentials of

the porphyrins as well as the rate of electron transfer. Kadish et al. found that when

electron-withdrawing substituients were placed on the phenyl rings of TPP, reductions

were easier and oxidations were more difficult.83 Korovin et al.84 studied the effects of

porphyrins with different aromatic substituents on the luminescence of ytterbium

compounds. They reported that the quantum yields of porphyrins with pyridine or










quinoline meso-subsituents are higher than in the case of phenyl substituents. By

incorporating methoxy, alkoxy and pyridyl groups into our porphyrin complexes, we

sought to study the effects of both electron donating and withdrawing groups on our

device efficiency. The goal was to identify a lanthanide complex that would promote

balanced injection, transport and recombination of charge carriers.

Synthesis

The synthesis of the ytterbium monoporphyrinate complexes began with the

reaction of the dilithiated porphyrins with Yb(C1)3(THF)3 under anhydrous, oxygen free

conditions to give the metallated porphyrin (Figure 3.1).51 The Yb(porphyrin)Cl

complexes, YbTmPP(C1)DME (14), YbTPPoeh(C1)DME (19), and YbTPyP(C1)DME

(22) were then allowed to react with the potassium salt of the desired axial ligand to give

the final products Yb(TmPP)Tp (15), Yb(TPPoeh)Tp (20) and Yb(TPyP)L(OEt)3 (23),

(Figure 3.2).5


Cl

Yb-O
NNe 2Li (DME) YbCl3(THF),

R Toluene R
N ON (DMF)
N R

R
R

OMe





OMe
14 19 22

Figure 3.1: Synthesis of YbTmPP(C1)DME (14), YbTPPoeh(C1)DME (19), and
YbTPyP(C1)DME (22).









The reaction to metallate the substituted porphyrin ligands with ytterbium

proceeded smoothly via nucleophilic displacement of chloride from YbC13. Differences

in the solubility of the reactants and products necessitated differences in the reported

procedures. For example, the TpyP compounds were found to be insoluble in most

solvents and the syntheses of these compounds were carried out in dry DMF. After

stirring Li2TpyP(DMF) (21) with Yb(C13)(THF)3 in DMF at reflux to give

YbTPyPCl(DMF), the solution was removed in vacuo and the crude material washed

several times with DME to remove any soluble impurities. Addition of the axial ligand,

LOEt, alleviated the solubility issues of the TpyP compounds. Once the halide was

replaced with LOEt, the compound was cleanly isolated in high yields by fractional

recrystallization from CH2C12. On the other hand, the TPPeoh complexes were found to

be extremely soluble in most organic solvents, including pentane. These compounds

were isolated as oils by extracting the residues of the reactions with pentane and

subsequent solvent removal under reduced pressure.










H EtO OEt
B EtO-P-Co-P-OEt

9( 1 l) NIC> C1 OX \EtO^ OE 0

RYb=Oe 15

R 20N
N N ,N

R -R

OMe
23
R- -\ OMe 15

OMe /r





Figure 3.2: Synthesis of Yb(TmPP)Tp (15), Yb(TPPoeh)Tp (20) and Yb(TPyP)L(OEt)3
(23).

NMR Studies

The complexes were characterized by proton NMR, UV/VIS spectroscopy as well

as by elemental analysis. Uncertainty about the magnitude of the contact and

pseudocontact shift in these new paramagnetic compounds adds difficulty to assigning

the NMR peaks, but using the relative integration of the peaks and what we have learned

from similar structures 85 facilitated assignment of the spectra. The proton NMR spectra

ofYbTmPP(C1)DME (14) and Yb(TPyP)L(OEt)3 (23) are shown in figures 3.3 and 3.4,

respectively. Assuming that rotation of the phenyl rings on the porphyrin ligand is slow

on the NMR timescale,68'85 compound 14 should have eight peaks. Of the eight, three

correspond to the methoxy groups on the phenyl ring and have an integration of 12 each,

two with a relative integral of 4 each correspond to the protons on the phenyl rings, two

with relative integrals of 6 and 4, correspond to the coordinated DME and one with an

integration of 8 is assigned to the pyrrole protons on the porphyrin. Using these






51


integration, peaks A and C were assigned to the protons on the phenyl ring, peaks D, E

and F were assigned to the methoxy groups on the phenyl ring while the remaining peaks,

G and H, arise from the coordinated DME. Similar to the analysis of compound 14, the

proton peaks in the NMR spectrum of 23 were assigned to protons via their relative

integration. Of the nine peaks, two are the diasteriotopic protons of the methylene on

the L(OEt) ligand and have integration of 6, one with an integration of 18 represents the

methyl protons on the ligand, one with an integration of 5 is the Cp ring. There are four

peaks assigned to the pyridyl ring and one to the pyrrole with integration of 4 and 1,

respectively (Figure 3.4).


G

C E
C10

R Yb -O




N F
D MeO A /
N R D G
E MeO--- /
F MeO B

R *
B
C

SI .I
16 14 12 10 8 6 4 2
Figure 3.3: Proton NMR spectrum of Yb(TmPP)Cl(DME) (14) in DMSO-d6 (*).









I

EtO P_ O OEt
-. O HG
EtO-P -o-P-0- FG


EtO Et

Yb


Py\ P/ iS\ Cy D

ZN N

PY 1' YC H

B
D I
B

F .
A ,C D E

18 16 14 12 10 8 6 4 2 0 -2 -4
Figure 3.4: Proton NMR of Yb(TPyP)L(OEt)3 (23) in C6D6(* denotes silicon grease
impurity).

Electrochemistry

Cyclic voltammetry is a useful technique for electrochemical studies of new

systems and provides valuable information on rates of oxidations/reductions as well as

the HOMO/LUMO band gap of the compound. While CH2C12 for example, is a common

solvent used in organic electrochemistry, it can only be used for potentials as high 1.8 V

and as low as -1.9 V vs. Ag/Ag Ionic liquids, on the other hand allow a much wider

potential window for electrochemical studies. Furthermore, these solvents have the

added advantage of not requiring a supporting electrolyte since they are inherently strong

ionic conductors.86'87










The electrochemical characterization studies of the lanthanide-porphyrin complexes

along with their free base porphyrins were performed in the ionic liquid, 1-Butyl-1-

methyl-pyrrolidium bis(trifluoromethyl)sulfonamide ([BMP+]-[NTF-]) (Figure 3.5) in

order to increase the available potential window (Figure 3.6). Electrochemical

investigations were performed in a three-electrode cell with a platinum counter wire,

platinum working disk and silver wire pseudo-reference electrode. Additionally,

ferrocene (Fc) was used as an internal reference standard. The insolubility of compound

Yb(TPPoeh)Tp (20) in [BMP+]-[NTF-] prevented the study of its electrochemistry.

O F


F F
F F



Figure 3.5: 1-Butyl-l-methyl-pyrrolidium bis(trifluoromethyl)sulfonamide ([BMP+]-
[NTF-]), ionic liquid used for electrochemical studies.



40
30
20
S 10
-- V
S 10


40








Figure 3.6: Cyclic voltamogram of [BMP+]-[NTF-].

A cyclic voltammogram is characterized by several important parameters. These

observables include the peak currents (ipa and ipc) and the corresponding peak potentials
observables include the peak currents (ipa and ipc) and the corresponding peak potentials










(Epa and Epc) and provide the basis for analyzing the cyclic voltammetric response. A

typical reduction process is expressed as:

O + ne- Rn-

If R- is easily oxidized back to O upon reversing the direction of the potential scan,

the process is said to be Nernstian reversible, giving the characteristic current versus

potential plot seen in figure 3.7. From a CV, the potentials at which redox reactions

occur, the reversablilty and stability of the oxidized and reduced species as well as the

HOMO/LUMO band gaps can be determined. Under ideal conditions, for a mass-

transport limited reversible process the peak potential separation (Epa Epc) is equal to

59/n mV (at 250 C) for all scan rates, the peak current ratio (ipa/ipc) is equal to 1 for all

scan rates and the peak current function increases linearly as a function of the square root

of the scan rate. The average of Epa and Epc gives E1/2 of the redox waves. The band gap

is thus the difference between the first oxidation/reduction wave and the E1/20f the first

reduction/oxidation wave.



15



.10,


1 0. 07 0.5 0.3
Potential (V vs AgfAgCl)
Figure 3.7: CV of a reversible reduction and reoxidation.

Previously reported cyclic voltammograms of LnTPP(acac) complexes consisted of

two oxidation waves with E1/2 of 0.7 and 0.9 V and two reduction waves with E1/2 of









-1.32 and -1.68 V (vs. SCE).47 Those waves correspond to four reversible one-electron

transfer process, with the electrode mechanism shown in figure 3.8.


nTPP(anTP nTPP-acac) LnTPP(acac) e [LnTPP(acac e [LnTPP(acac 2-

Figure 3.8: Electrode reaction mechanism of LnTPP(acac).

The cyclic voltammogram of TmPP in [BMP+]-[NTF-] at a scan rate of 0.1 V/s is

shown in figure 3.9. The first reduction/oxidation wave, peak B is reversible with a ipc/ipa

equal to one and Epa Epc equal to 79 mV (under the conditions, the peak potential

difference is equal to 110 mV for the Fc/Fc+ coupling, a well established completely

reversible process). The E1/2 for TmPP were determined to be -1.54 V and -1.78 V for

the two reduction waves and 0.66 V for the oxidation wave. The band gap is 2.2 eV.



8.0 -

6.0 C

4.0 B

2.0 A

0-

S -2.0

S -4.0

-6.0

-8.0

-10.0
1.6 1.2 0.8 0.4 0 -0.4 -0.8 -1.2 -1.6 -2.0

Potentiil V
Figure 3.9: CV of TmPP in ionic liquid with a scan rate of 0.1 V/s (* indicates Fc/Fc+).










Figure 3.10 shows a similar cyclic voltammogram of the complex YbTmPPTp (15)

in [BMP+]-[NTF-] at a scan rate of 0.3 V/s. Similar to LnTPP(acac) complexes, there are

two reduction waves, however there is only one oxidation wave. The first

reduction/oxidation wave, peak B is reversible with a ipc/ipa equal to one and Epa Epc

equal to 250 mV (under the conditions, the peak potential difference is equal to 260 mV

for the Fc/Fc+ coupling, a well established completely reversible process). Compared to

YbTPP(acac) with E1/2 of-1.76V and 0.28 V (vs. Fc/Fc+) for the first reduction and

oxidation, respectively, the E1/2 for complex 15 were determined to be -1.52 V and -1.97

V for the two reduction waves and 0.68 V for the oxidation wave. The band gap is

2.2 eV.


2.4 -
1.8 B
1.2
,*r 0.6


S -06 06
-12


-2.4
-3. .. ........... i .
-3.0
1.8 1.2 06 0 -0.6 -1.2 -1.8 -2.4
Potentijil / V
Figure 3.10: Cyclic voltammogram of 15 in ionic liquid with a scan rate of 0.3 V/s (
indicates Fc/Fc+).

The cyclic voltammogram of the free base porphyrin, TPyP is shown in figure 3.11.







57


3.5
3.0
2.5
2.0
1.5
1.0
0.5
0 /

-1.0



-3.0
-3.5
-4.0
-4.5
1.6 1.2 0.8 0.4 0 -0.4 -0.8 -1.2 -1.6

Potential / V


Figure 3.11: Cyclic voltammogram of TPyP in ionic liquid with a scan rate of 0.3 V/s.

There is one irreversible reduction/oxidation peak with E1/2 determined to be -1.62

V. There is also one irreversible oxidation/reduction peak and the E1/2 was determined to

be 0.71 V.

The cyclic voltammogram of the reduction and the oxidation for YbTPyP(LOEt)

(23) is in figure 3.12. In the reduction half, there are two reduction/oxidation waves, A

and B. Peak A is reversible with ipc/ipa equal to one and Epa Epc equal to 85 mV (under

the conditions, the peak potential difference is equal to 131 mV for the Fc/Fc+ coupling).

There are no reversible oxidation waves present, however, there are several poorly

resolved irreversible waves at 0.22 V and 0.85 V. The E1/2 were determined to be -1.69

V and -2.12 V for the two reduction wave. The band gap is 1.9 eV.







58


20 21


12A -
-10 0.9
-20 06


4-0
-0.6
0 -0 .9


2.0 1 8 16 14 1.2 1 0 08 06 0.4 02 0 0 -02 -0.4 -0 -. 1 0 -1.2 -1 4 -1.6 -1 8 -2.(
Potential V Potenti;tl, V


Figure 3.12: Cyclic voltammogram of the oxidation (left) and reduction (right)
ofYbTPyP(LOEt) in ionic liquid with a scan rate of 0.3 V/s.



The cyclic voltammogram of YbTPPTp is in figure 3.13. There are two


oxidation/reduction waves, A and B, and two reduction/oxidation waves, C and D, which


are quasi reversible. The E1/2 were determined to be -1.53 V and -1.91 V for the two


reduction waves and 0.51 V for the oxidation wave. The band gap is 2.0 eV.




2.4






06




-1.2



-2.4

-3.0
1.6 1.2 0.8 0.4 0 -0.4 -0.8 -1.2 -1.6 -2.0

Pt4lulli. /'l V1-
Figure 3.13: Cyclic voltammogram of YbTPPTp in ionic liquid with a scan rate of 0.2
V/s (* indicates Fc/Fc+).






59


Figure 3.14 shows the cyclic voltammogram of the complex YbTPP(LOEt) in

[BMP+]-[NTF-]. Similar to LnTPP(acac) complexes, there are two reduction waves and

two oxidation waves. The oxidation /reduction waves, peaks A and B are reversible with

Epa Epc equal to 75 and 68 mV, respectively (under the conditions, the peak potential

difference is equal to 75mV for the Fc/Fc+ coupling, a well established completely

reversible process). Peaks C and D are quasi reversible and peak E is irreversible. The

E1/2 for complex YbTPP(LOEt) were determined to be -1.79 V for the first reduction

wave and 0.35 V for the first oxidation wave. The band gap is 2.2 eV.


2.4 I. I I .
2.1
1.8 -
D
1.5
1.2
S 0.9 c
0.6 B
S 0.3
0
V -0.3 N
-0.6 E
-0.9
-1.2
1.8 1.2 0.6 0 -0.6 -1.2 -1.8 -2.4

Potential / V
Figure 3.14: Cyclic voltammogram ofYbTPP(LOEt) in ionic liquid with a scan rate of
0.05 V/s (* indicates Fc/Fc+).









Table 3.1 shows the half wave potentials and the band gap determined by the

electrochemical studies of the lanthanide complexes and the corresponding free base

porphyrins. When compared to TmPP, the redox potentials of 15 are quite similar,

suggesting that reductions are occurring on the macrocycle and addition of the metal ion

and Tp does not affect the electrochemistry. When comparing 15 to other Ln-porphyrin

complexes such as YbTPPTp, YbTPP(LOEt) and YbTPP(acac) the oxidation reaction is

not reversible and occurs at a higher potential, suggesting that substituents may destablize

the oxidation products. Similar to 15, the oxidation and reduction of 23 are affected by

the substituent. Comparing 23 with YbTPP(LOEt),reduction of the complex occurs at a

lower potential while the oxidation process is irreversible.

Comparing YbTPP(L) with different capping ligands also shows changes in the

reduction and oxidation potentials. Reported results show that the CV of YbTPP(acac)

has two reversible reduction and two reversible oxidation reactions. Complex

YbTPP(Tp) has two reduction and two oxidation reactions, which occur at higher

potentials and are not reversible. Complex YbTPP(LOEt) has two reduction and two

reversible oxidation waves as well as another oxidation peak, which irreversible.









Table 3.1: Half wave potentials and band gaps of Ln-porphyrin complexes (potentials are
reported vs Fc/Fc+ internal standard)a Irreversible peak and so was determined
by Ep.


Complex Red, E1/2 (v) Ox, E1/2 (v) Eg (eV)

1 2 1 2
TmPP -1.54 -1.78 0.66 2.6

Yb(TmPP)Tp (15) -1.52 -1.97 0.68 2.2

TPyP -1.62 0.71 2.3
YbTPyP(LOEt) (23) -1.69 -2.12 0.22 a 1.9

TPP (ionic liquid) -1.78 0.51 2.3

YbTPP(Tp) -1.53 -1.92 0.51 2.0

YbTPP(LOEt) -1.79 -2.31 0.35 0.7 2.1

YbTPP(acac) 47 -1.76 0.28 2.0

TPP in CH2C12 83 -1.64 -1.99 0.58 0.83 2.02

ZnTPP in CH2Cl2 83 -1.76 -2.15 0.34 0.65 2.1


Photoluminescence and Electroluminescene Studies

After the synthesis and full characterization of the substituted ytterbium porphyrin

complexes, the photoluminescence (PL) and electroluminescence (EL) properties of these

compounds were examined. The photoluminescence studies by Garry Cunnigham

showed photoluminescence from the metal-basedf-states (2F5/2 2F7/2) with efficiencies

ranging from 0.9% for YbTPPQ to 4.1% for YbTmPPTp. With the exception of

YbTPPQ, PL efficiencies were similar to other YbTPP complexes and higher than other

reported Yb-complexes, with efficiencies reported in the range of 0.1%88 to 0.8%.72 The

emission spectral properties for all of the porphyrin complexes were nearly identical,









with emission maxima at -980 and -1020 nm, similar to the previous YbTPP complexes

studied. Light emitting diodes containing blends of the substituted Yb-porphyrin

complexes and polystyrene were prepared. The configuration of all devices tested was

ITO/PEDOT-PSS/PS-porphyrin complex/Ca;Al 40:100:5:200 (nm).




hI


850 900 950 1000 1050
Wavelength / nm

Figure 3.15: Electroluminescence of Yb(TMPP)TP (bottom), Yb(TPyP)L(OEt)3 (middle),
and Yb(TPPoeh)TP (top) as a function of increasing voltage, starting at 6 V to
20 V.

Electroluminescence spectra of devices containing a 2:3 wt. ratio

(complex:polymer) of the porphyrin complexes dispersed in polystyrene show the -980

nm emission of the Yb3+ 2F5/2 > 2F7/2 transition as also seen in the PL measurements with

a weaker peak at -920 nm which is attributed to the crystal field splitting of the Yb3+f-

states by the axial and porphyrin ligands (Figure 3.15). The Yb(TPyP)LOEt devices


__ __: _




Z
r
-~









were considerably less stable and failed at a lower voltage than devices fabricated from

the other porphyrin complexes. The external quantum efficiency for each of the

complexes is -1-3 x 10-4which is similar to devices constructed with Yb(TPP)TP.73

Summary

Lanthanide-porphyrin complexes have been synthesized and characterized with a

variety of porphyrin-phenyl ring substituents in order to improve the efficiency of

electron transport and consequently the luminescence of our devices. The

electrochemistry of these complexes and the free base porphyrins were studied. The

lanthanide complexes show a decrease in the reduction/oxidation potentials when

compared with the unsubstitued YbTPPTp and YbTPP(LOEt) complexes and there is

little interpretable data for the oxidation of YbTPyP(LOEt), suggesting that the

substiuents affect the stability of the oxidized complexes. These electrochemical studies

also showed that changing the capping ligand affects the electrochemistry of the

complexes. PL and EL studies, however, show NIR luminescence with no change in

device efficiencies. Because there appears to be no correlation between the

electrochemical results and device efficiency suggests that the factors involved in device

construction outweigh any differences that arise from the identity of the porphyrin

substituents. So, for PL and EL studies, changing the porphyrin-phenyl ring substituents

has little effect on the electronic properties of the complex and does little to enhance

device efficiency.

Lanthanide-Phthalocyanine Complexes

Like TPP, phthalocyanine (Pc) (Figure 3.16) is an aromatic tetradentate macrocycle

with a strong absorption at -720 nm. Because of these properties, lanthanide complexes









of Pc were synthesized to investigate their luminescence properties and compare them

with the LnTPP complexes.






NN
N H N
N H
/ N





Figure 3.16: Phthalocyanine (Pc).

There are many examples of LnPc2 sandwich-type complexes in the literature.89-91

These complexes however, have a strong interligand charge transfer band at 1550 nm that

would quench many of the NIR emissions under investigation.92'93 In order to use Pc as a

chromophore for the lanthanides, a convenient synthesis of the monoPc complexes would

be desirable.

Synthesis and Structure of LnPc(LOEt) Complexes

The LnPc complexes were made with a methodology that was similar to that used

for the LnTPP complexes. Dilithiophthalocyanine was synthesized by refluxing 1,2

dicyanobenzene and lithium in pentanol. The synthesis of LnPcC1, which is published in

the patent literature,94 consists of refluxing Li2Pc with anhydrous LnC13 in dry DME.

The LnPcCl(DME) complex was then in turn used to synthesize the LnPc(LOEt)

complex. This procedure has been used to make the Ho, Er, Tm, and Yb complexes. The

synthesis of LnPcTP was attempted, but the product was insoluble in all organic solvents

and therefore purification and characterization was not completed.










In order to make NdPcI(DME) (24) and PrPcI(DME) (25), Li2Pc was was stirred at

reflux with the lanthanide triiodide complex in DME for twelve hours (Figure 3.17).

These complexes are insoluble in DME and were isolated by filtration.


2 Li(DME)


LnI3 4THF


DME

reflux, 4h


Ln = Nd, Pr
Figure 3.17: Synthesis ofLnPcI(DME), Ln= Nd, Pr.

The (LOEt) complexes were then synthesized by reaction of LnPcI(DME) with

K(LOEt) in THF at room temperature for twelve hours (Figure 3.18).


LnPcI(DME)


RO OR

II I
RO OR


THF
rt, 12h


Ln Nd,Pr
R CH2CH3 N N



Figure 3.18: Synthesis of LnPc(LOEt) complexes, Ln = Pr, Nd.

The LnPc(LOEt) compounds were recrystallized from CH2C12 and pentane and

were isolated in high yields and purity. A thermal ellipsoid plot of PrPc(LOEt) (27) is

shown in Figure 3.19.











C27A C26A
C27C25


C19A 06A
Co1 07A 01 C 024



C1707 C22A





N4A N2A


C15 C1 C2
C182






C14 C3
C9 C8
C10 N3 C7
C13 C11 C4
C12 C6 C5


Figure 3.19: Solid state structure of PrPc(LOEt) (27).

The complex is located on a mirror plane, which passes through Pr, Co, two N

atoms on the Pc ring and C on the Cp ring. This plane, however, does not pass through

any of the P atoms on the ligand, but between them causing them to occupy different

positions and creating disorder. Due to considerable amount of disorder associated with

the three OP(OC2H5)2 groups on the ligand, a drawing was used to model the crystal

structure. Bond lengths of Pr-N(2A) and Pr-N(4A) are 2.466(2) A and 2.468(2) A

respectively. The metal sits 1.459(2) A above the plane defined by N(2), N(2A), N(4)

and N(4A). In order to accommodate the large metal, the rings of N(2) and N(4) become

distorted with deviations from the plane of 10.6 and 5.3 respectively. When compared

to the crystal structure of YbPc(LOEt),92 the Pr sits 0.212(2) A further from the plane,

due to the larger ionic radius of Pr.










NMR Studies

As demonstrated with the TPP complexes, one and two-dimensional proton NMR

spectra were used to identify the PC complexes. The proton NMR spectrum of

PrPc(LOEt) (27) in figure 3.20 has 5 peaks (labeled A-E) with relative integrals of

5:8:8:12:18, respectively. With these relative integrals, the peaks were assigned as peak

A corresponding to the Cp protons, peaks B and C to the protons on the Pc ring, and

peaks D and E to the methylene and methyl protons on the ethoxy group respectively.

There is no separation of the diastereotopic protons of the methylene in the Pr complex.

The COSY spectra in figures 3.21 and 3.22 confirm the assignments made, showing one

set of cross peaks between peaks B and C and another between peaks D and E,

confirming the peak assignments from the 1-D spectra.




A

EtO OEt
EtO P-Co-P- O
II E
O D
Et 0 t D






-tN N0 E
SA


I I l I I I I I I I I I I I I I II I I1 I I l

LB 16 14 12 10 8 6 4 2 0 -2 -4


Figure 3.20: 1H NMR spectrum of PrPc(LOEt) (27).














-2








I-



16.


r


B-C


vI ... "I- MI'" -" 1 -"9I'' .... "... '"'I 1---- .1-I' I1.. ..I 1,i ... I" I
It 16 14 12 10 8 6 4 2 0 -2 -4
F1 (ppm)
Figure 3.21: COSY NMR spectra of PrPc(LOEt) (27).


72.
(ppn4
-4-




-a
1-
I-
2-


4-


aP S D-E


-


... I I I I I I '
5 4 3 2 1 0 -1 -2 -3 -4 -5
F1 (pPM)


Figure 3.22: Expansion of COSY NMR spectra of PrPc(LOEt) (27).

Photoluminescence Studies

PL studies were done by Gary Cunningham. Results show that there was no

photoluminescence for either the neodymium or the praseodymium complexes. The









triplet state of Pc is -1050 nm and is too low in energy to sensitize neodymium and

praseodymium. Similar results were obtained with Ho-, Tm- and YbPc(LOEt)

complexes. PL studies of ErPc(LOEt) observe the expected emission -1500nm,

however, the emission was extremely weak and no devices have been fabricated because

of the extremely low intensity of this emission.92

Summary

The series of LnPc monomeric complexes was completed with the synthesis of

neodymium and praseodymium complexes. These complexes were charactized by 1-D

and 2-D NMR spectroscopy and crystallography. Unfortunately, PL studies show no

observable luminescence for the Pr-,Nd-Ho- and TmPc(LOEt) complexes.

Experimental

Materials and Reagants

Unless otherwise stated, all syntheses were carried out on a double manifold

Schlenk line under an atmosphere of nitrogen or in a N2 filled glovebox. Glassware was

oven dried prior to use. Methylene chloride, dimethoxyethane, chloroform and

dimethlyforamide were purchased from Fisher Scientific and were dried with an

appropriate drying agent.7 The complexes

(Cyclopentadienyl)tris(diethylphospinito)cobalt(I) (LOEt),78 and hydridotris(1-

pyrazolyl)borate (TpH)79 were synthesized according to literature procedure.

Tetrapyridylporphyrin (TpyP), pyrrole, 2-ethylhexyl bromide, 3-hydroxybenzaldehyde

and 8-hydroxyquinoline were purchased from Aldrich and used as received. Tetra(3,4,5

trimethoxyphenyl) porphyrin (TmPP) was synthesized by the reaction of

trimethoxybenzaldehyde and pyrrole in refluxing propionic acid.95 Lithiated TmPP81 and

PC92 were prepared using literature procedures. Elemental analyses were performed at









the University of California, Berkley, Micro-Mass Facility or University of Florida

Spectroscopic Services. Proton NMR spectra were measured at 300 MHz at room

temperature unless otherwise stated, on Varian, Gemini 300, VXR 300, Mercury 300 or

Bruker 300 NMR spectrometers. Chemical shifts in spectra were referenced to residual

solvent peaks and are reported relative to tetramethylsilane. Electrochemical

investigations were carried out in an argon filled glove box using a three electrode cell

with a platinum wire, platinum working and silver wire reference electrodes with the

ionic liquid, 1-butyl-1-methyl-pyrrolidium NTF [BMP+-NTF-] (synthesized by Tony

Burrell, Los Alamos National Lab) as the electrolyte solution. Electrochemical data were

recorded using the electrochemical analyzer CHI730A-software. All UV/VIS spectra

were run in 1 cm square quartz cuvettes in CH3C1 (unless stated otherwise). The samples

were prepared and run under N2 on a double-beam Cary-100 UV-visible spectrometer.

Synthesis

Yb(TMPP)CI(DME) (14)

A Schlenk flask was charged with Li2TmPP(DME) (1 g, 0.9 mmol) and

YbCl3(THF)3 (0.5 g, 0.9mmol) in a glovebox. After the addition of 40 mL of dry

toluene, the flask was removed from the glovebox and the purple solution was refluxed

under N2. The progress of the reaction was monitored by UV/VIS and after 4 hours, the

Soret band at 415 nm had shifted to 425 nm indicating complete metalation of the

porphyrin. Toluene was removed under reduced pressure and the purple solid residue

was extracted and filtered with dry CH2C12 (2 x 30 mL). The combined extracts were

reduced in volume to ca. 20 mL and layered with pentane (ca. 20mL) giving 0.8 g of

purple product (64%). H NMR (300 MHz, DMSO): 63.25 (wl/2 = 2 Hz, 6 H, DME),

3.43(wi/2= 2Hz, 4 H, DME), 3.82 (wl/2= 4 Hz,12 H, -OCH3), 5.10 (wl/2= 2 Hz,12H, -









OCH3), 6.07 (wl/2= 5 Hz,12H, -OCH3) 7.89 (wl/2= 10 Hz,4H, H -ortho), 14.74 (wl/2 =

20 Hz, 8H, H-pyrrole), 15.75 (wl/2 = 24 Hz,4H, H -ortho). UV/VIS (CH2C12) Xmax (log

E): 425 (5.27), 513 (3.77), 552 (4.34), 588 (3.81) nm. Anal. Calc. for C60H62N4014C1Yb:

C, 56.69; H, 4.88; N, 4.41. Found: C, 56.58; H, 4.85; N, 4.32.

Yb(TMPP)Tp (15)

A solution of Yb(TmPP)Cl(DME) (0.lg 0.07 mmol) in DMF (ca. 40 mL) was

stirred while potassium hydridotris(1-pyrazolyl)borate (KTp) (0.02 g, 0.07 mmol) was

added. The purple solution was allowed to stir at room temperature in the glove box for

12 hours. The solvent was removed in vacuo and the purple solid was extracted with ca.

30 mL of CH2C12 and then filtered, leaving behind a brown residue. The purple solution

was reduced in volume to ca. 10 mL and then layered with ca. 20 mL of pentane. After

standing overnight, 0.08 g (71% yield) of purple product was collected. 1H NMR (300

MHz, C6D6): 622.69 (wl/2 = 79.41 Hz, 3H, H-Tp), 14.82 (wl/2 =18.83 Hz, 4H, H-ortho),

14.25 (wl/2 =15.97 Hz, 8H, H-pyrrole), 7.48 (wl/2 =14 Hz, 4H, H-ortho), 5.21 (wl/2 =12

Hz, 12 H, H- OCH3), 5.08 (wl/2 =6 Hz, 12H, H-OCH3), 4.61 (wl/2 =12 Hz, 3H, H-Tp),

3.27 (wl/2 =10 Hz, 12H, H- OCH3), -2.87(wl/2 = 12 Hz, 3H, H-Tp). UV/VIS (CH2C12)

,max (log E): 426 (3.11), 515 (0.22), 554 (0.39), 591 (0.20) nm. Anal. Calc. for

C65H62N10o12Yb: C, 57.44; H, 4.60; N, 10.31. Found: C, 57.77; H, 4.60; N, 10.31.

4(2-ethylhexyloxy)benzaldehyde (16)96

Ethylhexyl bromide (5.64 mL, 0.032 mol) was added dropwise to a solution of 4-

hydroxybenzaldehyde (3.89 g, 0.032 mol) and potassium carbonate (6.6 g, 0.048 mol) in

butanone in air. The solution was refluxed for four days after which time the brown

reaction mixture was filtered through CeliteTM and the solvent removed to give brown oil.

The oil was dissolved in ether (ca. 20 mL), washed with 1M NaOH (2 x 30 mL) then H20









(2 x 30 mL,) and dried (Na2SO4). Purification by column chromatography [silica,

methylene chloride: petroleum ether (3:2)] gave a yellow oil in 45% yield (3.54g,

1.51mmol). 1HNMR (300 MHz, acetone): 510.17 (s, 1H), 8.15 (d, J=3 Hz, 2H), 7.37 (d,

J=1.8 Hz, 2H), 4.28 (d, J=5.4 Hz 2H), 1.8-1.59 (m, 9H), 1.25-1.16 (m, 6H). 1C: (190.5,

164.7, 132.1, 130.5, 115.2, 71.11, 39.7, 30.8, 29.45, 29.40, 29.39, 24.15, 23.36, 14.16,

11.19.

5,10,15,20-tetrakis [4-(2-ethylhexyloxy) phenyl]-porphyrin (TPPoeh) (17)

To a boiling solution of propionic acid, ethylhexyloxybenzaldehyde (2.5 g, 0.01

mol) and pyrrole (0.7 mL, 0.01 mol) were added together giving a solution that turned

from yellow to dark brown. The solution was refluxed for one hour and the solvent was

removed under reduced pressure, leaving a brown solid. The compound was then

purified by column chromatography (silica, chloroform). The purple band was collected

and was reduced in volume to ca. 10 mL and then layered with ca. 20 mL of methanol to

give 17 in 5% yield (0.51 g, 0.4 mmol). 1H NMR (300 MHz, CDC13): 68.87 (s, 8H, H-

pyrrole), 8.12 (d, J=8.7 Hz, 8H, H-phenol), 7.29 (d, J=11.7 Hz 8H, H-phenol), 4.15 (d,

J=5.4 Hz, 8H), 1.95 (m, 8H), 1.73-1.43 (m, 28H), 1.08 (t, J =15 Hz, 12H), 0.99 (t, J=13.8

Hz, 12H) -2.76 (s, 1H). UV/VIS (CHC13) ,max (log E): 421(5.09), 520(4.06), 556(3.93),

595(3.63), 651(3.72) nm. Anal. Calc. for C75H92N404 : C, 80.89; H, 8.33; N, 5.03.

Found: C, 79.11; H, 8.56; N, 4.73.

Li2TPPoeh(DME)4 (18)

In a Schlenk tube, the addition of lithium hexamethyldisilazide (0.07 g, 0.46 mmol)

to TPPoeh, 17, (0.27 g, 0.23 mmol) in dry DME (ca. 20 mL) gave a color change from

purple to blue/green. The progress of the reaction was monitored by UV/VIS and after 3

hours, the Soret band at 421 nm had shifted to 434 nm indicating complete lithiation of









the porphyrin. The solution was removed in vacuo and the product was extracted with

pentane (2 x 20 mL), filtered, and cooled to -330 C to give 6 in 83% yield (0.278g). 1H

NMR (300 MHz, C6D6): 69.26 (s, 8H, H-pyrrole), 8.39 (d, J=8.1 Hz, 8H, H-phenol),

7.33 (d, J=8.1 Hz, 8H, H-phenol), 3.96 (d, J=5.4 Hz, 8H, H-OCH2), 2.12 (s, 18H, DME),

2.04 (s, 12H, DME), 1.88-1.38 (m, 36H), 1.03-0.96 (m, 24H). UV/VIS (CH2C12) Xmax

(log E): 434(4.74), 573(3.94), 618(2.79) nm. Anal. Calc. for C91H130 Li2 N4012: C,

73.56; H, 8.82; N, 3.77. Found: C, 72.12; H, 8.28, N, 4.22.

YbTPPoehC1(DME) (19)

To a solution of 18 (0.1 g, 0.07 mmol) in toluene (ca. 20 mL), YbCl3(THF)3 (0.06

g, 0.13 mmol) was added. Upon addition of YbC13, the solution turned from dark blue to

red. The solution was refluxed under N2 and the progress of the reaction was monitored

by UV/VIS. After 3 hours of refluxing, the Soret band had shifted to 421 nm, indicating

complete metalation of the porphyrin. The solvent was then removed in vacuo and the

product extracted with pentane (2 x 20 mL). The solvent was removed, leaving purple oil

in 70 % yield (0.07 g). 1H NMR (300 MHz, C6D6): 646.41 (wl/2 =123 Hz, 6H, DME),

15.45 (wl/2 =28 Hz, 8H, H-pyrrole), 14.86 (wl/2 =30 Hz, 4H, H-phenol), 9.585 (wl/2 =20

Hz, 4H, H-phenol), 9.24 (wl/2 =19 Hz, 4H, H-phenol), 8.31 (wl/2 =20 Hz, 4H, H-phenol),

4.83 (wl/2 =10 Hz, 8H, H-OCH2), 2.49-1.37 (m, 60H), -17.43 (wl/2 =240 Hz, 4H, DME).

UV/VIS (CH2C12) X)ax (log E): 421(5.27), 515(3.86), 554(4.14), 594(3.92) nm.

YbTPPoeh(Tp) (20)

In the glovebox, KTp (0.015 g, 0.056 mmol) was added to a stirring solution of 19

(0.07 g, 0.056 mmol) in toluene (ca. 20 mL). The purple solution was stirred overnight

and then the solvent removed in vacuo. The product was extracted with pentane (2 x 10

mL) and then filtered. The pentane solution was removed, giving 20 as red oil in 58%









yield (0.05 g). 1HNMR (300 MHz, C6D6): 622.7(wi/2 =120 Hz, 3H. H-Tp), 15.33 (wl/2

=60 Hz, 4H, H-phenol), 14.29 (wl/2 =30 Hz, 8H, H-pyrrole), 9.56 (wl/2 =45 Hz, 4H, H-

phenol), 8.19 (wl/2 =90 Hz, 8H, H-phenol), 4.91 (wl/2 =24 Hz, 8H, H-OCH2), 4.80 (wl/2

=27 Hz, 3H, H-Tp), 2.53-1.57 (m, 60H), -2.76 (wl/2 =45 Hz, 3H, H-Tp). UV/VIS

(CH2C12) )ax (log E): 424(4.83), 515(3.17), 555(3.77), 594(3.25) nm.

Li2TPyP(DMF)2 (21)

In the glovebox, lithium hexamethyldisilazide (0.86 g, 5.17 mmol) was added to a

solution of TpyP (0.8, 1.3 mmol) in dry DMF (ca. 30 mL), which changed colors from

red to green/blue. The solution was refluxed under N2 for 12 hours. After the reaction,

the solvent was removed in vacuo and the product was washed 3 times with ca. 20 mL of

hexane to remove the excess lithium hexamethyldisilazide. 1H NMR (300 MHz, DMSO-

d6): 68.93 (d, J=4.8Hz, 8H, H-phenol), 8.54 (s, 8H, H-pyrrole), 8.16 (d, J=6Hz, 8H, H-

phenol), 7.96 (s, 2H, DMF), 2.87(s, 6H, DMF), 2.72 (s, 6H, DMF). UV/VIS (CH2C12)

L~ax (log E): 434(5.34), 535(2.19), 575(3.34), 615(3.11) nm. Anal. Calc. for

C46H38NioO2Li2: C, 71.13; H, 4.93; N, 18.03. Found: C, 70.20; H, 4.44; N, 17.77.

YbTPyPCI(DME) (22)

In the glovebox, YbCl3(THF)3 (0.12 g, 0.25 mmol) was added to a solution of 21

(0.15 g, 0.25 mmol) in DMF (ca. 20 mL). The solution was refluxed for 12 hours under

N2 over which time the reaction mixture went from blue/green to red in color. The DMF

was removed in vacuo and the red product was washed 3 times with ca. 20 mL of DME

to give 0.15g (61% yield) of product. The poor solubility of this compound made it

difficult to purify completely and so it was used as is for the next reaction. 1H NMR (300

MHz, DMSO-d6): 616.29 (wl/2 =78 Hz, 4H, H-phenol), 14.71 (wl/2 =60 Hz, 8H, H-

pyrrole), 11.71 (wl/2 =60 Hz, 4H, H-phenol), 10.07 (wl/2 =60 Hz, 4H, H-phenol), 8.67









(wl/2 =60 Hz, 4H, H-phenol), 3.39 (12H, DME), 3.22 (18H, DME). UV/VIS (CH2C2)

,ax (log E): 425 (5.00), 513(3.45), 555(4.00), 593(3.40) nm. Anal. Calc. for

C44H36ClN8O2Yb: C, 57.61; H, 3.96; N, 12.22. Found: C, 50.80; H, 3.88; N,11.80.

YbTPyP(LOEt) (23)

In the glovebox, K(LOEt) (0.11 g, 0.18 mmol) was added to a solution of 22 (0.2 g,

0.18 mmol) in DMF (ca. 10 mL) and stirred for 12 hours. The solution was then

removed in vacuo and the desired product was extracted with CH2C12 (2 x. 10 mL). The

CH2C12 extractions were filtered and reduced in volume to ca. 10 mL and then layered

with ca. 20 mL of pentane to give 23 as a red powder in 41% yield (0.1 g). 1HNMR

(300 MHz, C6D6): 516.86 (wl/2 =72 Hz, 4H, H-phenol), 15.37(wl/2 =12 Hz, 8H, H-

pyrrole), 12.03 (wl/2 =76 Hz, 4H, H-phenol), 10.11 (wl/2 =80 Hz, 4H, H-phenol), 8.31

(wl/2 =36 Hz, 4H, H-phenol), 7.91 (wl/2 =30 Hz, 6H, H-OCH2CH3), 7.34 (wl/2 =35 Hz,

6H, H-OCH2CH3), 2.83 (wl/2 =12 Hz, 18H, H-OCH2CH3), -4.86 (wl/2 =6 Hz, 5H, H-Cp).

UV/VIS (CH2C12) Xmax (log E): 425 (5.24), 510(3.95), 555(4.07), 593(3.69) nm. Anal.

Calc. for C57H55N8O9YbP3Co: C, 51.82; H, 4.19; N, 8.48. Found: C, 49.51; H, 3.95; N,

8.02.

NdPcI(DME) (24)

NdI3(THF)4 (0.25g 0.31mmol) and Li2Pc (0.162g, 0.31mmol) were added together

in 40 mLofDME. The blue solution was refluxed for 12 hours under N2. The solution

was cooled to room temperature at which time the solvent was removed via canula

filtration. 0.126 g (0.143 mmol, 47%) of product was isolated after filtering and drying on

the Schlenk line. The complex is insoluble in all organic solvents, preventing full

characterization of this material. It was used as is for the next reaction.









PrPcI(DME) (25)

The same procedure for 24 was used in this synthesis. To Prl3(THF)4 (1.00 g, 1.2

mmol), and Li2PC (0.65 g, 1.2 mmol), 50 mL of DME was added and refluxed for 12

hours to give 0.695 g (0.8 mmol, 65%) of 25.

NdPc(LOEt) (26)

NdPcI(DME) (0.160 g, 0.18 mmol) and the K(LOEt) (0.09 g, 0.18 mmol) were

stirred together in 30 mL of dry THF. After 12 hours, the blue solution was removed in

vacuo and the solid was extracted with about 30 mL CH2C12, leaving behind a white

residue of KI. The volume of the CH2C12 solution was reduced to 15 mL and then

layered with pentane and allowed to sit at room temperature until the product crystallized.

After 48 hours, the blue product was isolated in 65% yield (0.142 g, 0.119 mmol) via

cannula filteration. 1H NMR (C6D6): 311.51 (w1/2 = 5.15 Hz, 5H, H-Cp), 6.35 (w/2 =

13.36 Hz, 8H, H-Pc), 6.30 (wl/2 = 12.64 Hz, 8H, H-Pc), -0.69 (wl/2 = 31.27 Hz, 6H,

OCH2CH3), -0.98 (wl/2 = 32.34 Hz, 6H, OCH2CH3), -2.14 (wl/2 = 12.67 Hz, 18H,-

OCH2CH3). UV/VIS (CH3C1), Xmax (log E) = 676(5.05), 644(2.85), 608(4.29), 342(3.86)

nm. Anal. Calc. for C49H5109N8P3CoNd: C, 49.37; H, 4.31; N, 9.40. Found: C,48.25;

H,4.16; N,8.73.

PrPc(LOEt) (27)

PrPcI(DME) (0.2 g, 0.2 mmol) was allowed to react with K(LOEt) (0.135 g, 0.230

mmol) in dry THF (ca. 20 mL) for 12 hours under inert atmosphere. The solution was

removed in vacuo and the complex was extracted with ca. 30 mL of CH2C12. The volume

of the blue solution was reduced to ca. 10 mL and layered with pentane (ca. 20 mL),

causing the compound to precipitate. The product was isolated in 71.3% yield (0.195 g,

0.16 mmol). H NMR (C6D6): 317.48(w/2 = 5.61 Hz, 5H, H-Cp), 5.10(w1/2 = 11.65 Hz,









8H, H-Pc), 4.04(wl/2 = 11.60 Hz, 8H, H-Pc), -3.27(wl/2 = 46.90 Hz, 12H, OCH2CH3), -

4.08(wl/2 = 13.18 Hz, 18H, OCH2CH3). UV/VIS (CH3CI), Xmax (log E) = 674(4.97),

644(4.19), 610(4.23), 340(4.58) nm. Anal. Calc. for C49H51O9N8P3CoPr: C, 49.51; H,

4.32; N, 9.43. Found: C, 50.42; H, 4.22; N, 8.95.

HoPc(LOEt) (28)

To a dark blue solution of HoPcCl(DME) (0.125 g,0.155 mmol) in 30 mL of THF,

was added K(LOEt) (0.08 g,0.15 mmol). After stirring at room temperature for 12 hours,

the solution was removed in vacuo and the product was extracted with CH2C12 (3 x 10

mL). The extracts were combined and the volume of the solution was reduced to ca. 10

mL and then layered with pentane. The blue crystals were collected in 38% yield (0.08 g,

0.065 mmol) after 12 hours. 1H NMR (C6D6): 353.54(Wl/2= 64.22 Hz, 5H, H-Cp), -

4.85(wl/2= 17.62 Hz, 8H, H-Pc), -15.17(wl/2= 51.41 Hz, 8H, H-Pc), -16.98(wl/2= 64.4

Hz, 18H, OCH2CH3), -24.02(wl/2= 15.63 Hz, 6H, OCH2CH3), -26.01 (wl/2= 16.69 Hz,

6H, OCH2CH3). UV/VIS (CH3C1), Xmax (log E) 672(5.72), 642(4.41), 606(5.00),

340(5.20) nm. Anal. Calc. for C49H51O9N8P3CoHo: C, 48.53; H, 4.24; N, 9.24. Found: C,

47.52; H, 4.17; N, 8.0.

TmPc(LOEt) (29)

Using the same procedure as 28, TmPcCl(DME) (0.148 g, 0.206 mmol) and

K(Klaui) (0.097 g, 0.206 mmol) were stirred together in THF to give 0.05 g (0.041 mmol,

20% yield). 1H NMR (C6D6): 348.62(Wl/2 = 62.53 Hz, 6H, OCH2CH3), 47.86(wl/2=

19.41 Hz, 8H, H-Pc), 47.56(w/2 = 83.07 Hz, 6H, OCH2CH3), 27.62(w/2 = 18.41 Hz,

18H, OCH2CH3), 27.02(w/2 = 10.22 Hz, 8H, H-Pc), -71.83(w/2 = 16.69 Hz, 5H, H-Cp).

UV/VIS (CH3CI), Xmax (log E)= 675(5.08), 673(5.17), 645(4.48), 608(4.41), 338(4.65)









nm. Anal. Calc. for C49H51O9N8P3CoTm: C, 48.37; H, 4.22; N, 9.21. Found: C,48.10; H,

4.10; N,8.79.

XRAY of PrPc(LOEt)

Data were collected at 173 K on a Siemens SMART PLATFORM equipped with A

CCD area detector and a graphite monochromator utilizing MoKa radiation (k = 0.71073

A). Cell parameters were refined using up to 8192 reflections. A full sphere of data

(1850 frames) was collected using the co-scan method (0.30 frame width). The first 50

frames were remeasured at the end of data collection to monitor instrument and crystal

stability (maximum correction on I was < 1 %). Absorption corrections by integration

were applied using the measured, indexed, crystal faces.

The structure was solved by Direct Methods in SHELXTL5, and refined using full-

matrix least squares. The non-H atoms were treated anisotropically, whereas the

hydrogen atoms were calculated in ideal positions and were riding on their respective

carbon atoms. The complex is located on a mirror plane which causes a disorder in the

OP(OC2H5)2 ligand bridging the Pr and Co centers. The mirror passes through Pr, Co,

two N atoms on opposite side the macrocycle, and atom C25 of the cp ring and bisects

the bond between C27 and its mirror equivalent C27a. The mirror symmetry does not

pass through any of the P atoms but between them causing them to occupy six positions

belonging to two parts of the three OP(OC2H5)2 ligands rotated by an angle of 600 from

each other. A total of 374 parameters were refined in the final cycle of refinement using

18773 reflections with I > 2o(I) to yield R1 and wR2 of 3.46% and 5.45%, respectively.

Refinement was done using F2














CHAPTER 4
POLYERMIZABLE LANTHANIDE-PORPHYRIN COMPLEXES

Introduction

Because our systems work without a conjugated polymer, devices were prepared by

spin-casting YbTPP(L) as the only active layer. These devices, however had poor film

quality when compared with blended devices and produced only 20% of the near-infrared

intensity of devices consisting of blends of 5 mol% metal complexes with non-cojugated

polymers.97 So, blending our complexes with a polymer, conjugated or non-conjugated

enhances device efficiency probably by minimizing self-quenching effects and by

improving film quality.

Blending polymers with metal complexes acting as emitting molecules has been

shown to be a valuable technique in the development of efficient sources of light for

LEDs. There are, however, some disadvantages to using this technique. The blending of

a polymer and dopant usually results in phase separation and non-uniform dispersion of

the dopant which can lead to lower luminescent efficiencies and device durability due to

triplet-triplet annihilation and higher turn on voltages.98 Minimizing phase separation

should result in enhanced device performance.

Lanthanide Polymers

One way to improve film quality is to incorporate the dopant into the polymer.99

Ling et al. coploymerized an Eu(vinylbenzoic acid) (thenoyltrifluoroacetone)

(phenathroline) complex with a vinylcarbozole to obtain an Eu-containing copolymer for

red LEDs (Figure 4.1).100






























Figure 4.1: Eu(TTA)2(VBA)phen-NVK copolymer.

The copolymer was prepared by free radical copolymerization of the two

monomers, using AIBN as an intiator, with average molecular weights around

10,000 g/mol. Electroluminescent studies on the single-layered device produced red

emission with a performance that compared favorably with those of other single layered

devices and a completely homogeneous film. Other efforts to make Ln-copolymers

include work by Zeng et al. who conducted EL studies on a Tb-containing polymer that

produces green light 101 and work by Yang et al. who conducted EL studies on a Tb-Eu

copolymer in which varying the ratio of Eu/Tb tunes the emission color.102

Porphyrin Polymers

In recent years, porphyrin oligomers and polymers have been studied for

applications in sensing, non-linear optic materials, catalysts and artificial

photosynthesis.103 One example of a porphyrin polymer was reported by Haber and

coworkers, who synthesized a porphyrin supported on a polyaniline system for studying










its catalytic activity towards the co-oxidation of styrene and iso-butyraldehyde (Figure

4.2).104


H
/N


H
N


Figure 4.2: Structure of porphyrin supported in polyaniline.

Other examples consist of the copolymerization of porphyrin monomers,

incorporating the porphyrin in the backbone of the polymer or as a pendant group (Figure

4.3).105,106

While there has been considerable research on the incorporation of lanthanides,

porphyrins, and transition metalloporphyrins into polymer systems, there are no

lanthanide-porphyrin polymer systems, perhaps due to the lack of convenient synthesis of

suitable lanthanide porphyrin monomers. This chapter will discuss the synthesis of

polymerizable lanthanide-porphyrin complexes in efforts to incorporate the complex into

polymers.











-C-
H2


0

Ph

Figure 4.3: Examples of porphyrin polymers.


Lanthanide-Porphyrin Polymer Complexes

Lanthanide-vinylporphyrin Complexes

Synthesis

The vinyl porphryin, 5-(4-vinylphenyl)- 10,15,20 triphenylprophyrin (TPPv) was

synthesized in order to be co-polymerized into a polymer to study the effects of changes

in phase segregation on device efficiency. The porphyrin was synthesized by one-pot

mixed aldehyde condensation reaction between vinylbenzaldehyde, pyrrole and

benzaldehyde, using BF3(OEt2) cocatalysis (Figure 4.4). After stirring the mixture for an

hour, oxidation by DDQ afforded a mixture of porphyrin isomers. The desired

compound was isolated via column chromotagraphy, packing the column with silica gel

and hexanes and eluding the desired porphyrin from CH3Cl/hexanes. No other

combinations of the condensation were isolated. After recrystallization from a

CH3Cl/methanol solution, TPPv (30) was collected in 14% yield.









Ph
H O
H

N HCH3C1
1 + 3 + 4 4 Ph Ph
I1 I-J BF3(OEt)2 N










TPPv (30)

Figure 4.4: Synthesis of TPPv.

Lindsey and coworkers synthesized and isolated the vinylporphyrin metallated with

zinc with similar results.107 The same compound was recently synthesized by Pomogailo

et al. via a Wittig reaction between 5-(4-formylphenyl)10,15,20- triphenylporphyrin and

trimethylenephosphorane.108 This synthetic approach, however requires a multi-step

process with each stage of the reaction needing column chromotagraphy and

recrystallization to separate and purify the products. The reaction starts with the mixed

aldehyde condensation reaction to form a monocyanoporphyrin. After addition of zinc

acetate, the metallated porphyrin is reduced to the aldehyde. The zinc is then removed

and the free base porphyrin aldehyde is reacted with the ylide to form the vinylporphyrin

(Figure 4.5).










H O H 0 Ph
H

3 4 NH N


CN --=N HN
Ph

Ph I Zn(AcO)2

Ph Zn CHO Zn(TPP-CN)
---N N
Ph / Ph

Ph

SHC1

TPP-aldehyde Ylide HN


Ph

Figure 4.5: Synthesis of vinylporphyrin by Pomogailo et al.

With the vinyl porphyrin synthesized and characterized, similar synthetic

procedures as described in the previous chapters were carried out in order to metallate the

porphyrin. Firstly, the TPPv dianion was synthesized by reacting TPPv with lithium

hexamethyldisilazide in refluxing DME. In a salt metathesis reaction between the

dianion Li2TPPv(DME)2, (31) and YbCl3(THF)3, YbTPPv(C1)DME was synthesized.

After stirring the mixture of the Li salt and YbCl3(THF)3 for four hours at reflux, the

UV/VIS spectrum of the reaction mixture showed an absorption at -425 nm

corresponding to metallated TPPv. The solution was then separated from KC1 by hot

filtration and removal of the solvent. The complex YbTPPvCl(DME) (32) was

recrystallized from a mixture of CH2C12 and pentane to obtain the purple material in 80%

yield (Figure 4.6).











C--Yb--
Cl-Yb O


2Li(DME)2 ,--
Toluene
N eN + YbCl3(THF)3 --
reflux, 4hrs.
NN



YbTPPv(C1)DME (32)

Figure 4.6: Synthesis of 32.

In a second set of salt metathesis reactions, YbTPPv(C1)DME was allowed to react

with the capping ligands KTp or K(LOEt) to give YbTPPv(Tp) (33) or YbTPPv(LOEt)

(34) (Figure 4.7), respectively. In a Schlenk flask, YbTPPv(CL)DME and the capping

ligand were stirred at room temperature under nitrogen in DME. After stirring for twelve

hours, complexes 33 and 34 were extracted with CH2C12 and were then isolated as purple

crystalline solids in high yields by recrystallization from mixtures of CH2C12 and pentane.

The purity of the bulk material was confirmed by elemental analysis.


EtO OEt H
EtO-P--Co--POEt B
0 P 0NO
EtO 0/OEt N
EI I O DME
Yb DME K(LOEt) + Cl-b- + KTp DM Yb
rm temp, 12hrs rm temp, 12hrs

Ph Ph Ph Ph Ph Ph

N N N N N N

Ph /Ph N N Ph



YbTPPv(LOEt) (34) YbTPPv(Tp) (33)


Figure 4.7: Synthesis of complexes 33 and 34.










NMR studies

The 1H NMR spectrum of YbTPPvTP (33) is shown in figure 4.8. Similar to the

lanthanide porphyrin complexes discussed in previous chapters, the peaks were assigned

by using 1-D, 2-D and variable temperature NMR techniques. The 1-D spectrum shows

12 peaks, five of the peaks correspond to the protons from the phenyl rings, three of the

peaks correspond to the Tp protons, three of the peaks correspond to the vinyl group and

the twelfth peak corresponds to the pyrrole protons.












1 C
E K






4 23 2 21 20 19 18 17 1 1.5 14 13 1 11 10 9 0 7 5 4 6. 2 1 0 -
F / B G










Figure 4.8: 1H NMR spectrum of YbTPPvTp (33)

With relative integrals of three and a cross peak between K and L, as seen in the 2-

D spectrum of 33 (Figure 4.9), peaks A, K, and L are assigned to the protons on the Tp

ligand. Because of its proximity to the paramagnetic nucleus the relaxation time of peak

A is too short to allow the appearance of the crosspeaks between A and either K or L in

the NMR spectrum. Peaks B and H are assigned the ortho protons on the phenyl ring

with relative integrals of 4 and cross peaks between only peaks D and F, respectively.