Carbazole compounds as host materials for triplet emitters in organic light-emitting diodes: polymer hosts for high-efficiency light-emitting diodes

A carbazole homopolymer and carbazole copolymers based on 9,9'-dialkyl-[3,3']-bicarbazolyl, 2,5-diphenyl-[1,3,4]-oxadiazole and 9,9-bis(4-[3,7-dimethyloctyloxy]phenyl)fluorene were synthesized and their electrical and photophysical properties were characterized with respect to their application as host in phosphorescent polymer light-emitting diodes. It is shown that the triplet energy of a polymer depends on the specific connections between its building blocks. Without changing the composition of the polymer, its triplet energy can be increased from 2.3 to 2.6 eV by changing the way in which the different building blocks are coupled together. For poly(9-vinylcarbazole) (PVK), a carbazole polymer often used as host for high-energy triplet emitters in polymer light-emitting diodes, a large hole-injection barrier of about 1 eV exists due to the low-lying HOMO level of PVK. For all carbazole polymers presented here, the HOMO levels are much closer to the Fermi level of a commonly used anode such as ITO and/or a commonly used hole-injection layer such as PEDOT:PSS. This makes high current densities and consequently high luminance levels possible at moderate applied voltages in polymer light-emitting diodes. A double-layer polymer light-emitting diode is constructed comprising a PEDOT:PSS layer as hole-injection layer and a carbazole-oxadiazole copolymer doped with a green triplet emitter as emissive layer that shows an efficacy of 23 cd/A independent of current density and light output.     

High triplet energy polymer as host for electrophosphorescence with high efficiency

We report the conjugated polymer P(tBu-CBP) as a host with high triplet energy (E(T) 2.53 eV) and suitable HOMO (5.3 eV) and LUMO (2.04 eV) energy levels. Upon doping with green and red emission Ir-complexes, it gives devices with high luminous and external quantum efficiencies for green emission (23.7 cd/A, 6.57%) and for red emission (5.1 cd/A, 4.23%), respectively, and low turn-on voltage (3 V). For both devices, the efficiencies are higher than those of the corresponding devices with the same backbone P(3,6-Cz) as a host by a factor of 4, even though the latter has an E(T) (2.6 eV) slightly higher than that of the former. The results reflect that, in phosphorescent devices, the difference in E(T) between the host and guest is not the only factor that determines the device efficiency, and the present side group modification via the 9 position of carbazole also plays an important role, which allows a tuning of HOMO and LUMO levels to provide more balance in electron and hole fluxes and provides prevention from formation of excimer.     

三嗪类双极性蓝色磷光主体材料的合成及性能

设计合成了一种基于三嗪类的新型双极性蓝色磷光主体材料[4-(4,6-二-α-萘氧基-1,3,5-三嗪-2-基)苯基]9-咔唑(NOTPC),并对其结构进行了表征。通过紫外-可见(UV-Vis)吸收、荧光、低温磷光、循环伏安法、热重分析(TGA)、差热分析(DSC)和密度泛函理论(DFT)对其性能及结构进行了研究。结果表明,NOTPC在CH₂Cl₂稀溶液中的吸收峰位于341和374 nm;发射峰位于478 nm;NOTPC的低温(77 K)磷光光谱的第一发射峰位于442 nm,其三线态能级为2.80 eV,与蓝色磷光材料FIrpic(2.62 eV)的能级相匹配;NOTPC的HOMO主要分布在苯基咔唑单元,而LUMO主要定域在三嗪环上。其HOMO能级为-5.40 eV,与阳极ITO的功函(-4.5~-5.0 eV)相匹配,LUMO能级为-2.32 eV,接近于电子传输材料PBD(-2.82 eV),NOTPC表现出双极传导性能, 且热稳定性良好。     

Photoinduced intramolecular electron transfer and triplet energy transfer in a steroid-linked norbornadiene-carbazole dyad

Bichromophoric compound 3 beta-((2-(methoxycarbonyl)bicyclo[2.2.1]hepta-2,5-diene-3-yl)carboxy)androst-5-en-17 beta-yl-[2-(N-carbazolyl)acetate] (NBD-S-CZ) was synthesized and its photochemistry was examined by fluorescence quenching, flash photolysis, and chemically induced dynamic nuclear polarization (CIDNP) methods. Fluorescence quenching measurements show that intramolecular electron transfer from the singlet excited state of the carbazole to the norbornadiene group in NBD-S-CZ occurs with an efficiency (Phi SET) of about 14 % and rate constant (kSET) of about 1.6 x 10(7) s-1. Phosphorescence and flash photolysis studies reveal that intramolecular triplet energy transfer and electron transfer from the triplet carbazole to the norbornadiene group proceed with an efficiency (TET + TT) of about 52 % and rate constant (kTET + kTT) of about 3.3 x 10(5) s-1. Upon selective excitation of the carbazole chromophore, nuclear polarization is detected for protons of the norbornadiene group (emission) and its quadricyclane isomer (enhanced absorption); this suggests that the isomerization of the norbornadiene group to the quadricyclane proceeds by a radical-ion pair recombination mechanism in addition to intramolecular triplet sensitization. The long-distance intramolecular triplet energy transfer and electron transfers starting both from the singlet and triplet excited states are proposed to proceed by a through-bond mechanism.     

Energy transfer and triplet exciton confinement in polymeric electrophosphorescent devices

Energy transfer and triplet exciton confinement in polymer/phosphorescent dopant systems have been investigated. Various combinations of host‐guest systems have been studied, consisting of two host polymers, poly(vinylcarbazole) (PVK) and poly[9,9‐bis(octyl)‐fluorene‐2,7‐diyl] (PF), blended with five different phosphorescent iridium complexes with different triplet energy levels. These combinations of hosts and dopants provide an ideal situation for studying the movement of triplet excitons between the host polymers and dopants. The excitons either can be confined at the dopant sites or can flow to the host polymers, subject to the relative position of the triplet energy levels of the material. For PF, because of its low triplet energy level, the exciton can flow back from the dopants to PF when the dopant has a higher triplet energy and subsequently quench the device efficiency. In contrast, efficient electrophosphorescence has been observed in doped PVK films because of the high triplet energy level of PVK. Better energy transfer from PVK to the dopants, as well as triplet exciton confinement on the dopants, leads to higher device performance than found in PF devices. Efficiencies as high as 16, 8.0, and 2.6 cd/A for green, yellow, and red emissions, respectively, can be achieved when PVK is selected as the host polymer. The results in this study show that the energy transfer and triplet exciton confinement have a pronounced influence on the device performance. In addition, this study also provides material design and selection rules for the efficient phosphorescent polymer light‐emitting diodes. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2681–2690, 2003     

Efficient π‐conjugated interrupted host polymer by metal‐free polymerization for blue/green phosphorescent light‐emitting diodes

A new aromatic host polymer poly{[1,4‐bis(9‐decylcarbazole‐3‐yl)‐2,3,5,6‐tetrafluorobenzene‐3,3′‐diyl]‐alt‐[N‐methylisatin‐2‐one‐3,3‐diyl]} (PICzFB) containing carbazole–tetrafluorinebeneze–carbazole moiety in the π‐conjugated interrupted polymer backbone was synthesized by superacid‐catalyzed metal‐free polyhydroxyalkylation. The resulted copolymer PICzFB showed a comparatively wide band gap up to 3.32 eV and high triplet energy (E_T) of 2.73 eV due to confined conjugation by the δ? C bond interrupted polymer backbone. Blue and green light‐emitting devices with PICzFB as host, FIrpic and Ir(mppy)₃ as phosphorescent dopants showed the maximum luminous efficiencies of 5.0 and 27.6 cd/A, respectively. The results suggested that the strategy of incorporating bipolar unit into the π‐conjugated interrupted polymer backbone can be a promising approach to obtain host polymer with high triplet level for solution‐processed blue and green phosphorescent polymer light‐emitting diodes. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1037–1046     

Effective shielding of triplet energy transfer to conjugated polymer by its dense side chains from phosphor dopant for highly efficient electrophosphorescence

To examine the quenching of a triplet exciton by low triplet energy (E(T)) polymer hosts with different chain configurations for high E(T) phosphor guests, the quenching rate constant measurements were carried out and analyzed by the standard Stern-Volmer equation. We found that an effective shielding of triplet energy transfer from a high E(T) phosphor guest to a low E(T) polymer host is possible upon introducing dense side chains to the polymer to block direct contact from the guest such that the possibility of Dexter energy transfer between them is reduced to a minimum. Together with energy level matching to allow charge trapping on the guest, high device efficiency can be achieved. The extent of shielding for the systems of phenylene-based conjugated structures from iridium complexes follows the sequence di-substituted (octoxyl chain) in the para position (dC8OPPP) is greater than monosubstituted (mC8OPPP) and the PPPs with longer side chains are much higher than a phenylene tetramer (P4) with two short methyl groups. Further, capping the dialkoxyl-susbstituents with a carbazole (Cz) moiety (CzPPP) provides enhanced extent of shielding. Excellent device efficiency of 30 cd/A (8.25%) for a green electrophosphorescent device can be achieved with CzPPP as a host, which is higher than that of dC8OPPP as host (15 cd/A). The efficiency is higher than those of high E(T) conjugated polymers, poly(3,6-carbazole) derivatives, as hosts (23 cd/A). This observation suggests a new route for molecular design of electroluminescent polymers as a host for a phosphorescent dopant.     

Conversion of intramolecular singlet electron transfer at room temperature into triplet energy transfer at 77 K: photoisomerization in norbornadiene- and carbazole-labeled poly(aryl ether) dendrimers

A series of Fréchet-type poly(aryl ether) dendrimers (CZ-Gn-NBD, n = 1-3) with carbazole (CZ) chromophores and a norbornadiene (NBD) group attached to the periphery and the core, respectively, were synthesized, and their photophysical and photochemical properties were investigated. Selective excitation of the carbazole units in CZ-Gn-NBD resulted in a singlet electron transfer from CZ to NBD at room temperature, and an intersystem crossing followed a triplet-triplet energy transfer from CZ to NBD in glassy 2-methyltetrahydrofuran at 77 K. Both singlet electron transfer and triplet energy transfer processes lead to the isomerization of the norbornadiene group into the quadricyclane (CZ-Gn-QC). The efficiencies and the rate constants for singlet electron transfer are approximately 88, 80, and 74% and 1.8 x 10(9), 6.1 x 10(8), and 4.0 x 10(8) s(-1) for generations 1-3, respectively. The quantum yields of the intramolecular photosensitized isomerization are measured to be approximately 0.013, 0.012, and 0.011, and the efficiencies of triplet norbornadiene formation via singlet electron transfer are approximately 0.070, 0.065, and 0.059 for generations 1-3, respectively. The light-harvesting ability of CZ-Gn-NBD increases with the generation due to an increase of the number of peripheral chromophores. In glassy 2-methyltetrahydrofuran at 77 K, the triplet-triplet energy transfer proceeds with efficiencies of approximately 0.86, 0.64, and 0.36 and rate constants of 0.96, 0.25, and 0.08 s(-1) for generations 1-3, respectively. The intramolecular singlet electron transfer and triplet energy transfer in CZ-Gn-NBD proceed mainly via a through-space mechanism involving the proximate donor (folding back conformation) and acceptor groups.     

Carbazole endcapped heterofluorenes as host materials: theoretical study of their structural, electronic, and optical properties

By mimicking the molecular structure of 4,4'-bis(N-carbazolyl)-2,2'-biphenyl (CBP), which is a widely used host material, a new series of host molecules (carbazole-endcapped heterofluorenes, CzHFs) were designed by linking the hole-transporting carbazole to the core heterofluorene molecules in either meta or para positions of the heterofluorene. The aromatic cores considered in this study are biphenyl, fluorene, silafluorenes, germafluorenes, carbazole, phosphafluorene, oxygafluorene, and sulfurafluorene. To reveal their molecular structures, optoelectronic properties and structure-property relationships of the proposed host materials, an in-depth theoretical investigation was elaborated via quantum chemical calculations. The electronic structures in the ground states, cationic and anionic states, and lowest triplet states of these designed molecules have been studied with emphasis on the highest occupied molecular orbitals (HOMOs), the lowest unoccupied molecular orbitals (LUMOs), energy gaps (E(g)), triplet energy gaps ((3)E(g)), as well as some other electronic properties including ionization potentials (IPs), electron affinities (EAs), reorganization energies (λ), triplet exciton generation fraction (χ(T)), spin density distributions (SD), and absorption spectra. These photoelectronic properties can be tuned by chemical modifications of the heteroatom and the carbazole substitution at different positions. This study provides theoretical insights into the nature of host molecules, and shows that the designed CzHFs can meet the requirements of the host materials for triplet emitters.     

Synthesis and characterization of a polyfluorene containing carbazole and oxadiazole dipolar pendent groups and its application to electroluminescent devices

We have synthesized a blue‐light‐emitting polyfluorene (PF) derivative ( PF‐CBZ‐OXD ) that presents bulky hole‐transporting carbazole and electron‐transporting oxadiazole pendent groups functionalized at the C‐9 positions of alternating fluorene units. The results from photoluminescence and electrochemical measurements indicate that both the side chains and the PF main chain retain their own electronic characteristics in the copolymer. An electroluminescent device incorporating this polymer as the emitting layer was turned on at 4.5 V; it exhibited a stable blue emission with a maximum external quantum efficiency of 1.1%. Moreover, we doped PF‐CBZ‐OXD and its analogue PF‐TPA‐OXD with a red‐light‐emitting iridium phosphor for use as components of phosphorescent red‐light emitters to investigate the effect of the host's HOMO energy level on the degree of charge trapping and on the electrophosphorescent efficiency. We found that spectral overlap and individual energy level matching between the host and guest were both crucial features affecting the performance of the electroluminescence devices. Atomic force microscopy measurements indicated that the dipolar nature of PF‐CBZ‐OXD , in contrast to the general nonpolarity of polydialkylfluorenes, provided a stabilizing environment that allowed homogeneous dispersion of the polar iridium triplet dopant. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2925–2937, 2007     

Bipolar molecules with high triplet energies: synthesis, photophysical, and structural properties

This article sheds new light on the interplay of electronic and conformational effects in luminescent bipolar molecules. A series of carbazole/1,3,4-oxadiazole hybrid molecules is described in which the optoelectronic properties are systematically varied by substituent effects which tune the intramolecular torsion angles. The synthesis, photophysical properties, cyclic voltammetric data, X-ray crystal structures, and DFT calculations are presented. Excited state intramolecular charge transfer (ICT) is observed from the donor carbazole/2,7-dimethoxycarbazole to the acceptor phenyl/diphenyloxadiazole moieties. Introducing more bulky substituents onto the diphenyloxadiazole fragment systematically increases the singlet and triplet energy levels (E(S) and E(T)) and blue shifts the absorption and emission bands. The triplet excited state is located mostly on the oxadiazole unit. The introduction of 2,7-dimethoxy substituents onto the carbazole moiety lowers the value of E(S), although E(T) is unaffected, which means that the singlet-triplet gap is reduced (for 7bE(S) - E(T) = 0.61 eV). A strategy has been established for achieving unusually high triplet levels for bipolar molecules (E(T) = 2.64-2.78 eV at 14 K) while at the same time limiting the increase in the singlet energy.     

Novel tri-carbazole modified fluorene host material for highly efficient solution-processed blue and green electrophosphorescent devices

A series of novel solution-processable small-molecule host materials: 2DPF-TCz, 2SBF-TCz, 27DPF-TCz, and 27SBF-TCz comprising a fluorene monomer as the rigid core and tri-carbazole as the periphery have been designed and synthesized, and their optical, electrochemical, and thermal properties have been fully characterized. The host materials exhibit high glass-transition temperatures (231–310 °C) and high triplet energy levels (2.61–2.73 eV). High-quality amorphous thin films can be obtained by spin-coating the host materials from solutions. It is found that the HOMO level of the host materials can be tuned by linking the tri-carbazole unit to the 2,7 positions of the fluorine core, resulting in appropriate HOMO energy levels (−5.36 to −5.23 eV) for improved hole-injection in the device. Solution-processed blue and green electrophosphorescent devices bases on the developed host materials exhibit high efficiencies of 21.2 and 34.8 cd A⁻¹, respectively.     

Synthesis and properties of nitrogen‐linked poly(2,7‐carbazole)s as hole‐transport material for organic light emitting diodes

A novel class of carbazole polymers, nitrogen‐linked poly(2,7‐carbazole)s, was synthesized by polycondensation between two bifunctional monomers using the palladium‐catalyzed amination reaction. The polymers were characterized by ¹H NMR, Infrared, Gel permeation chromatography, and MALDI‐TOF MS and it was revealed that the combination of the monomer structures is important for producing high molecular weight polymers. Thermal analysis indicated a good thermal stability with high glass transition temperatures, e.g., 138 °C for the higher molecular weight polymer P2 . To pursue the application possibilities of these polymers, their optical properties and energy levels were investigated by UV‐Vis absorption and fluorescence spectra as well as their electrochemical characteristics. Although the blue light emission was indeed observed for all polymers in solution, the quantum yields were very low and the solid films were not fluorescent. On the other hand, the HOMO levels of the polymers estimated from the onset potentials for the first oxidation in the solid thin films were relatively high in the range of ?5.12 to ?5.20 eV. Therefore, light emitting diodes employing these polymers as a hole‐transport layer and iridium(III) complex as a triplet emitter were fabricated. The device of the nitrogen‐linked poly(2,7‐carbazole) P3 with p,p′‐biphenyl spacer, which has a higher HOMO level and a higher molecular weight, showed a much better performance than the device of P2 with m‐phenylene spacer. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3880–3891, 2009     

一种基于咔唑的新型磷光主体材料的合成及光电性能

设计并合成了一种基于咔唑的新型的磷光主体材料, 即9-(6-(9-咔唑基)己基)咔唑(hCP), 对其结构及性能进行了表征. 研究结果表明: hCP分子中两个咔唑与烷基链是非共平面的, 由于长烷基链的缠绕, 因而具有较高的三线态能级(3.01 eV)和较高的玻璃化温度(93℃); 以hCP为主体材料, 与绿光磷光染料三(2-苯基吡啶)合铱(Ir(ppy)₃)掺杂作为发光层, 制备了磷光电致发光器件, 其器件的最大电流效率为15.1 cd·A^-1, 相对于4,4'-N,N'-二咔唑基联苯(CBP)为主体材料的参考器件, 显著提高了34.8%.     

Soluble polynorbornenes with pendant carbazole derivatives as host materials for highly efficient blue phosphorescent organic light‐emitting diodes

We report novel host polymers for a high‐efficiency polymer‐based solution‐processed phosphorescent organic light‐emitting diode with typical blue‐emitting dopant bis(4,6‐difluorophenylpyridinato‐N,C²)iridium(III) picolinate (FIrpic). The host polymers, soluble polynorbornenes with pendant carbazole derivatives, N‐phenyl‐9H‐carbazole ( P1 ), N‐biphenyl‐9H‐carbazole ( P2 ), and 9,9′‐(1,3‐phenylene)bis‐9H‐carbazole (mCP) ( P3 ) are efficiently synthesized by vinyl addition polymerization of norbornene monomers using Pd(II) catalyst in combination with 1‐octene chain transfer agent. The polymers exhibit high thermal stability with high decomposition (T_d5 > 410 °C) and glass transition temperatures (T_g ≈ 268 °C). The HOMO (ca. ?5.5 to ?5.7 eV) and LUMO (ca. ?2.0 to ?2.1 eV) levels with the high triplet energy of about 2.7–3.0 eV suggest that the polymers are suitable for a host material for blue emitters. Among the solution‐processed devices that were fabricated based on the emissive layers containing the P1 ? P3 host doped with various concentrations of FIrpic (7–13 wt %), the best device with P3 host exhibits power efficiency of 3.0 lm W^?1 and external quantum efficiency of 4.0% at a luminance of 1000 cd m^?2 that is outstanding among the polymeric rivals. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Effects of Substitution Position of Carbazole-Dibenzofuran Based High Triplet Energy Hosts to Device Stability of Blue Phosphorescent Organic Light-Emitting Diodes

High triplet energy hosts were developed through the modification of the substitution position of carbazole units. Two carbazole-dibenzofuran-derived compounds, 9,9′-(dibenzo[b,d]furan-2,6-diyl)bis(9H-carbazole) (26CzDBF) and 4,6-di(9H-carbazol-9-yl)dibenzo[b,d]furan (46CzDBF), were synthesized for achieving high triplet energy hosts. In comparison with the reported hole transport type host, 2,8-di(9H-carbazol-9-yl)dibenzo[b,d]furan (28CzDBF), 26CzDBF and 46CzDBF maintained high triplet energy over 2.95 eV. The device performances of the hosts were evaluated with electron transport type host, 2-phenyl-4, 6-bis(3-(triphenylsilyl)phenyl)-1,3,5-triazine (mSiTrz), to comprise a mixed host system. The deep blue phosphorescent device of 26CzDBF:mSiTrz with [[5-(1,1-dimethylethyl)-3-phenyl-1H-imidazo[4,5-b]pyrazin-1-yl-2(3H)-ylidene]-1,2-phenylene]bis[[6-(1,1-dimethylethyl)-3-phenyl-1H-imidazo[4,5-b]pyrazin-1-yl-2(3H)-ylidene]-1,2-phenylene]iridium (Ir(cb)₃) dopant exhibited high external quantum efficiency of 22.9% with a color coordinate of (0.14, 0.16) and device lifetime of 1400 h at 100 cd m⁻². The device lifetime was extended by 75% compared to the device lifetime of 28CzDBF:mSiTrz (800 h). These results demonstrated that the asymmetric and symmetric substitution of carbazole can make differences in the device performance of the carbazole- and dibenzofuran- derived hosts.     

Rational Design of Poly(2,7‐Carbazole) Derivatives for Photovoltaic Applications

A reliable model that can be used to estimate the electronic properties (i.e., the HOMO, LUMO, and band gap energies) of conjugated polymers would be a great tool for applications in organic electronics such as light‐emitting diodes, field‐effect transistors, and photovoltaic cells. Recently, poly(2,7‐carbazole) derivatives have shown promising results when used as an active donor layer in bulk heterojunction photovoltaic cells with power conversion efficiency exceeding 7%. By using a simple correlation between density functional theory (DFT) theoretical calculations performed on six model compounds (using the repeating unit) and experimental data from the six corresponding polymers, an accurate estimation of the HOMO energy level, the LUMO energy levels, and the band gap of several poly(2,7‐carbazole) derivatives was obtained. According to the theoretical data obtained for more than one hundred repeating units, fourteen new copolymers that can be used as p‐type materials in bulk heterojunction solar cells were selected and synthesized. Experimental data obtained from these materials were then used to refine the correlation between DFT and experimental data of poly(2,7‐carbazole) derivatives.

     

Asymmetry in platinum acetylide complexes: confinement of the triplet exciton to the lowest energy ligand

To determine structure-optical property relationships in asymmetric platinum acetylide complexes, we synthesized the compounds trans-Pt(PBu3)2(C[triple bond]CC6H5)(C[triple bond]C-C6H4-C[triple bond]CC6H5) (PE1-2), trans-Pt(PBu3)2(C[triple bond]CC6H5)(C[triple bond]C-C6H4-C[triple bond]C-C6H4-C[triple bond]CC6H5) (PE1-3) and trans-Pt(PBu3)2(C[triple bond]C-C6H4-C[triple bond]CC6H5)(C[triple bond]C-C6H4-C[triple bond]C-C6H4-C[triple bond]CC6H5) (PE2-3) that have different ligands on either side of the platinum and compared their spectroscopic properties to the symmetrical compounds PE1, PE2 and PE3. We measured ground state absorption, fluorescence, phosphorescence and triplet state absorption spectra and performed density functional theory (DFT) calculations of frontier orbitals, lowest lying singlet states, triplet state geometries and energies. The absorption and emission spectra give evidence the singlet exciton is delocalized across the central platinum atom. The phosphorescence from the asymmetric complexes comes from the largest ligand. Time-dependent (TD) DFT calculations show the S1 state has mostly highest occupied molecular orbital (HOMO) --> lowest unoccupied molecular orbital (LUMO) character, with the LUMO delocalized over the chromophore. In the asymmetric chromophores, the LUMO resides on the larger ligand, suggesting the S1 state has interligand charge transfer character. The triplet state geometries obtained from the DFT calculations show distortion on the lowest energy ligand, whereas the other ligand has the ground state geometry. The calculated trend in the triplet state energies agrees very well with the experimental trend. Calculations of triplet state spin density also show the triplet exciton is confined to one ligand. In the asymmetric complexes the spin density is confined to the largest ligand. The results show Kasha's rule applies to these complexes, where the triplet exciton moves to the lowest energy ligand.     

Molecular design of efficient white‐light‐emitting fluorene‐based copolymers by mixing singlet and triplet emission

A new strategy to realize efficient white‐light emission from a binary fluorene‐based copolymer (PF‐Phq) with the fluorene segment as a blue emitter and the iridium complex, 9‐iridium(III)bis(2‐(2‐phenyl‐quinoline‐N,C³′)(11,13‐tetradecanedionate))‐3,6‐carbazole (Phq), as a red emitter has been proposed and demonstrated. The photo‐ and electroluminescence properties of the PF‐Phq copolymers were investigated. White‐light emission with two bands of blue and red was achieved from the binary copolymers. The efficiency increased with increasing concentration of iridium complex, which resulted from its efficient phosphorescence emission and the weak phosphorescent quenching due to its lower triplet energy level than that of polyfluorene. In comparison with the binary copolymer, the efficiency and color purity of the ternary copolymers (PF‐Phq‐BT) were improved by introducing fluorescent green benzothiadiazole (BT) unit into polyfluorene backbone. This was ascribed to the exciton confinement of the benzothiadiazole unit, which allowed efficient singlet energy transfer from fluorene segment to BT unit and avoided the triplet quenching resulted from the higher triplet energy levels of phosphorescent green emitters than that of polyfluorene. The phosphorescence quenching is a key factor in the design of white light‐emitting polyfluorene with triplet emitter. It is shown that using singlet green and triplet red emitters is an efficient approach to reduce and even avoid the phosphorescence quenching in the fluorene‐based copolymers. The strategy to incorporate singlet green emitter to polyfluorene backbone and to attach triplet red species to the side chain is promising for white polymer light‐emitting diodes. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 453–463, 2008     

Toward a rational design of poly(2,7-carbazole) derivatives for solar cells

On the basis of theoretical models and calculations, several alternating polymeric structures have been investigated to develop optimized poly(2,7-carbazole) derivatives for solar cell applications. Selected low band gap alternating copolymers have been obtained via a Suzuki coupling reaction. A good correlation between DFT theoretical calculations performed on model compounds and the experimental HOMO, LUMO, and band gap energies of the corresponding polymers has been obtained. This study reveals that the alternating copolymer HOMO energy level is mainly fixed by the carbazole moiety, whereas the LUMO energy level is mainly related to the nature of the electron-withdrawing comonomer. However, solar cell performances are not solely driven by the energy levels of the materials. Clearly, the molecular weight and the overall organization of the polymers are other important key parameters to consider when developing new polymers for solar cells. Preliminary measurements have revealed hole mobilities of about 1 x 10(-3) cm2 x V(-1) x s(-1) and a power conversion efficiency (PCE) up to 3.6%. Further improvements are anticipated through a rational design of new symmetric low band gap poly(2,7-carbazole) derivatives.