Soluble,saturated‐red‐light‐emitting poly(p‐phenylenevinylene) containing triphenylamine units and cyano groups

A conjugated poly(p‐CN‐phenylenevinylene) (PCNPV) containing both electron‐donating triphenylamine units and electron‐withdrawing cyano groups was prepared via Knoevenagel condensation in a good yield. Gel permeation chromatography suggested that the soluble polymer had a very high weight‐average molecular weight of 309,000. A bright and saturated red emission was observed under UV excitation in solution and film. Cyclic voltammetry showed that the polymer presented quasi‐reversible oxidation with a relatively low potential because of the triphenylamine unit. A single‐layer indium tin oxide/PCNPV/Mg–Ag device emitted a bright red light (633 nm). © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3947–3953, 2004     

Novel aromatic polyamides bearing pendent diphenylamino or carbazolyl groups

Two new diamines, 2,4‐diaminotriphenylamine ( 3 ) and N‐(2,4‐diaminophenyl)carbazole ( 4 ), were synthesized via the cesium fluoride‐mediated aromatic substitution reactions of 1‐fluoro‐2,4‐dinitrobenzene with diphenylamine and carbazole, followed by palladium‐catalyzed hydrazine reduction. Amorphous and soluble aramids having pendent diphenylamino and carbazolyl groups were prepared by the phosphorylation polycondensation of aromatic dicarboxylic acids with diamines 3 and 4 , respectively. The aramids derived from diamine 3 had sufficiently high molecular weights to permit the casting of flexible and tough films. They exhibited excellent mechanical properties and moderately high softening temperatures in the 221–298 °C range. However, the reactions of diamine 4 with aromatic diacids gave relatively lower molecular weights products that could not afford flexible films. For a comparative purpose, the parent aramids derived from m‐phenylenediamine and aromatic diacids were also prepared and characterized. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3302–3313, 2004     

PHOTOPHYSICAL STUDIES ON ORGANIC COMPOUNDS——TIME-RESOLVED TRANSIENT ABSORPTION SPECTRA STUDIES ON TRIPHENYLAMINE IN VARIOUS SOLVENTS

The transient absorption spectra of triphenylamine (TPA) in various solvents have beeninvestigated by the methods of nanosecond laser photolysis. The lifetimes of TPA were meas-ured. In hexane and ethanol, the transient absorptions of triplet state and triplet excimer ofTPA were observed. However, the transient absorptions of the TPA cation radical was alsoobserved in acetonitrile besides that of the triplet TPA monomer and excimer. According tothe experimental facts, the transient photophysical mechanism of TPA in various solvents hasbeen proposed.     

Synthesis and optical properties of a poly(p‐phenylenevinylene) derivative and polyfluorenes with bipolar groups along the main chain

A poly(p‐phenylenevinylene) derivative (PPV–TPA)] and a series of statistical copolyfluorenes (PF–TPA)] containing oxadiazole and triphenylamine segments along the main chain were synthesized by the Heck reaction and nickel‐mediated coupling, respectively. The PF–TPA copolyfluorenes with relatively low contents of oxadiazole and triphenylamine units were readily soluble in common organic solvents, whereas the other copolyfluorenes displayed lower solubility. PPV–TPA showed excellent solubility in solvents such as tetrahydrofuran (THF), dichloromethane, chloroform, and toluene. Thin films of the polymers absorbed light in the range of 375–396 nm and had optical band gaps of 2.76–2.98 eV. They emitted blue‐green light with a maximum at 414–522 nm. The fluorescence quantum yields in THF solutions were 0.08–0.53. The copolyfluorene PF–TPA thin films with high contents of oxadiazole and triphenylamine moieties emitted pure blue light that remained stable even after annealing at 150 °C for 4 h in air. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3556–3566, 2006     

Synthesis of novel side‐chain triphenylamine polymers with azobenzene moieties via RAFT polymerization and investigation on their photoelectric properties

Two novel and well‐defined polymers, poly[6‐(5‐(diphenylamino)‐2‐((4‐methoxyphenyl)diazenyl)phenoxy)hexyl methacrylate] (PDMMA) and poly[6‐(4‐((3‐ethynylphenyl)diazenyl) phenoxy)hexyl methacrylate] (PDPMMA), which bear triphenylamine (TPA) incorporated to azobenzene either directly (PDMMA) or with an interval (PDPMMA) as pendant groups were successfully prepared via reversible addition‐fragmentation chain transfer polymerization technique. The electrochemical behaviors of PDPMMA and PDMMA were investigated by cyclic voltammograms (CV) measurement. The hole mobilities of the polymer films were determined by fitting the J‐V (current‐voltage) curve into the space‐charge‐limited current method. The influence of photoisomerization of the azobenzene moiety on the behaviors of fluorescence emission, CV and hole mobilities of these two polymers were studied. The fluorescent emission intensities of these two polymers in CH₂Cl₂ were increased by about 100 times after UV irradiation. The oxidation peak currents (I_OX) of the PDMMA and PDPMMA in CH₂Cl₂ were increased after UV irradiation. The photoisomerization of the azobenzene moiety in PDMMA had significant effect on the electrochemical behavior, compared with that in PDPMMA. The changes of the hole mobility before and after UV irradiation were very small for both polymers. The HOMO energies (E_HOMO, HOMO: the highest occupied molecular orbital) of side chain moieties of TPA incorporated with cis‐isomer and trans‐isomer of azobenzene in PDMMA and PDPMMA were obtained by theoretical calculation, which are basically consistent with the experimental results. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Solution‐processable and thermally cross‐linkable fluorene‐cored triple‐triphenylamines with terminal vinyl groups to enhance electroluminescence of MEH‐PPV: Synthesis,curing, and optoelectronic properties

This study reports the synthesis, curing, and optoelectronic properties of a solution‐processable, thermally cross‐linkable electron‐ and hole‐blocking material containing fluorene‐core and three periphery N‐phenyl‐N‐(4‐vinylphenyl)benzeneamine ( FTV ). The FTV exhibited good thermal stability with T_d above 478 °C in nitrogen atmosphere. The FTV is readily cross‐linked via terminal vinyl groups by heating at 160 °C for 30 min to obtain homogeneous film with excellent solvent resistance. Multilayer PLED device [ITO/PEDOT:PSS/cured‐ FTV /MEH‐PPV/Ca (50 nm)/Al (100 nm)] was successfully fabricated using solution processed. Inserting cured‐ FTV is between PEDOT:PSS and MEH‐PPV results in simultaneous reduction in hole injection from PEDOT:PSS to MEH‐PPV and blocking in electron transport from MEH‐PPV to anode. The maximum luminance and maximum current efficiency were enhanced from 1810 and 0.27 to 4640 cd/m² and 1.08 cd/A, respectively, after inserting cured‐ FTV layer. Current results demonstrate that the thermally cross‐linkable FTV enhances not only device efficiency but also film homogeneity after thermal curing. FTV is a promising electron‐ and hole‐blocking material applicable for the fabrication of multilayer PLEDs based on PPV derivatives. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 000: 000–000, 2012     

Half‐sandwich Ruthenium (II) complexes with triphenylamine modified dipyridine skeleton and application in biology/luminescence imaging

Four half‐sandwich ruthenium^II (Ru^II) complexes with triphenylamine‐modifed dipyridine frameworks were synthesized and characterized. The cytotoxicity of target complexes toward A549 (lung cancer cells), HeLa (cervical cancer cells) and HepG2 (hepatoma cells) were obtained by the MTT assay, which were superior to cisplatin with the IC₅₀ values changed from 2.4 ± 0.1 μM to 9.2 ± 2.7 μM. Meanwhile, complexes possess the ability of antimetastasis to cancer cells. Ru^II complexes could be transported by serum albumin, catalyze the conversion of NADH (the reduced state of nicotinamide‐adenine dinucleotide) to NAD⁺ and induce the accumulation of reactive oxygen species, which confirmed the antineoplastic mechanism of oxidation. Ru^II complexes could enter A549 cells followed by a non‐energy dependent cellular uptake mechanism, target lysosomes with the Pearson's colocalization coefficient of 0.75, lead to lysosomal damage, disturb the cell cycle (S phase), and eventually induce apoptosis. The results demonstrate that these Ru^II complexes are potential anticancer agents with dual functions, including metastasis inhibition and lysosomal damage.     

Multifunctional triphenylamine polymers synthesized via direct (hetero) arylation polymerization

The design rules for creating multifunctional organic electronic materials are currently limited. By copolymerizing twisted triphenylamine (TPA) and electron rich dioxythiophene (XDOT) monomers via Direct (Hetero) Arylation Polymerization (DHAP), a set of polymers are obtained that perform as yellow to transmissive electrochromic (EC) films with up to 45% contrast, as well as in electroluminescent (EL) applications, achieving a luminance of ∼450 cd/m² in yellow‐green polymer light‐emitting diodes (PLEDs). In addition, polymerizing TPA with a donor‐acceptor‐donor monomer results in a low‐bandgap polymer that achieves power conversion efficiencies up to 2.5% when blended with PC₇₁BM in conventional organic photovoltaic (OPV) devices. Incorporation of TPA units into the polymer backbone largely breaks any aggregation and ordering in the solid‐state, leading to highly soluble materials that form smooth, reproducible thin films. The TPA unit also serves to break conjugation throughout the polymer backbone, providing precise control over optical and electronic properties through choice of comonomer. These results suggest that TPA copolymers can be useful for achieving multi‐functionality without sacrificing facile solution processability, making them promising candidates for multifunctional devices like dual EC/EL displays. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 147–153     

Synthesis, Characterization and Properties of Novel Star-Shaped π-Conjugated Oligomers with Triphenylamine Core

Four new star‐shaped π‐conjugated oligomers ( TPA‐CZ3 , TPA‐TPA3 , TPA‐PTZ3 and TPA‐BT3 ) with triphenylamine as a core and different electron‐donating ability groups, carbazole, triphenylamine, phenothiazine and bithiophene, as peripheral units have been designed and synthesized via the Heck reaction. These oligomers show good solubility in common organic solvents. Their photophysical, electrochemical, electronic structure and charge transfer properties between these star‐shaped π‐conjugated oligomers and N,N′‐bis(1‐ethylpropyl)‐3,4:9,10‐perylene bis(tetracarboxyl diimide) (EP‐PDI) have been investigated by UV‐vis absorption spectra, photoluminescence (PL) spectra, cyclic voltammetry (CV) measurement, theoretical calculations and fluorescence quenching. The results show that the absorptions and fluorescences of TPA‐CZ3 , TPA‐TPA3 and TPA‐PTZ3 are red shifted with the electron‐donating ability of the peripheral unit increasing from carbazole to triphenylamine and phenothiazine. In addition, although the bithiophene group has a weaker electron‐donating ability than carbazole, triphenylamine and phenothiazine, the absorption and fluorescence of TPA‐BT3 have a red shift than those of TPA‐CZ3 , TPA‐TPA3 and TPA‐PTZ3 because TPA‐BT3 has a longer conjugation length than TPA‐CZ3 , TPA‐TPA3 and TPA‐PTZ3 . The triphenylamine core and the peripheral units can constitute a large conjugated structure. The fluorescence quenching properties indicate that efficient charge transfer can happen between the star‐shaped oligomers and EP‐PDI.     

双态发光三苯胺基有机硼配合物的设计、合成与应用

以三(4-溴苯)胺、4-氨基苯硼酸频哪醇酯、4-二乙氨基水杨醛和三氟化硼乙醚溶液为原料,经过Suzuki偶联反应、缩合反应和配位反应,设计、合成了一种新型三枝结构的三苯胺有机硼配合物(TPAB),使用 ¹H和 ¹³C NMR对 TPAB的结构进行了表征,通过紫外可见吸收光谱和荧光发射光谱详细研究了TPAB溶液和固体态的光物理性能以及不同的外部条件对其发光性能的影响。发现 TPAB溶液和固体态都具有较强的荧光发射,在四氢呋喃溶液中的吸收峰位于 417 nm,发射峰位于 548 nm,荧光量子产率为 40.49%,荧光寿命为 1.72 ns;TPAB 固体的荧光发射峰位于 582 nm,荧光量子产率为 11.43%,荧光寿命为 0.72ns,表明TPAB具有优良的双光发光性能。此外,TPAB具有良好的发光稳定性,不受pH、金属离子、氨基酸和压力的影响。基于化合物优异的发光性能,将其应用于荧光细胞成像,在肝癌细胞(HepG2)中表现出良好的单光子和双光子荧光成像效果。