Syntheses of Conjugated Polymers for Photonics

Summary: By the Suzuki coupling reaction of 9,9-dioctyl-2,7-bis(1,3,2-dioxaborinan-2-yl)fluorene ( I ) and 3,5-di-tert-butylphenyl 2,5-dibromobenzenesulfonate ( II ) the alternating poly{[9,9-dioctylfluoren-2,7-diyl]-alt-[2-(3,5-di-tert-butyl-phenoxysulfonyl)-1,4-phenylene]} ( III ) was synthesized. Alkaline hydrolysis of III gave a conjugated polyelectrolyte carrying sulfonic acid groups ( IV ). Monomers 2,5-dibromo-3-[2-(pyren-1-yl)vinyl]thiophene and 2,5-dibromo-3-[2-(quinolin-4-yl)vinyl)thiophene were prepared and copolymerized with I to afford poly{[9,9-dioctylfluoren-2,7-diyl]-alt-[3-(2-(pyren-1-yl)vinyl)thiophen-2,5-diyl]} ( V ) and poly{[9,9-dioctylfluoren-2,7-diyl]-alt-[3-(2-(quinolin-4-yl)-vinyl)thiophen-2,5-diyl] ( VI ), respectively. Conjugated backbone of V contains the conjugated pyrene unit in the side chain. Similarly the side chain of VI contains the conjugated quinoline structure unit which can be for instance protonated. By the Suzuki polycondensation reaction of I and of the prepared methyl 3-(2,7-dibromocarbazole-9-yl)propionate ( VII ) the new poly{[9,9-dioctylfluorene-2,7-diyl]-alt-[9-(2-methoxycarbonylethyl)carbazole-2,7-diyl]} ( VIII ) was synthesized and characterized.     

New electron-donating segment to develop thermally activated delayed fluorescence emitters for efficient solution-processed non-doped organic light-emitting diodes

Thermally activated delayed fluorescent(TADF) materials capable of efficient solution-processed nondoped organic light-emitting diodes(OLEDs) are of important and practical significance for further development of OLEDs. In this work, a new electron-donating segment, 2,7-di(9 H-carbazol-9-yl)-9,9-dimethyl-9,10-dihydroacridine(2 Cz-DMAC), was designed to develop solution-processable non-doped TADF emitters. 2 Cz-DMAC can not only simultaneously increase the solubility of compounds and suppress har...     

Synthesis of fluorescent fluorene–isoindole-containing mono- and oligomers

Novel fluorene–isoindole-containing light-emitting mono- and oligomers were prepared. The synthesis of the monomers N-(4-bromo-phenyl)-2-(7-bromo-9,9-diethylfluoren-2-yl)-isoindole-1-carboxamide, N-(7-bromo-9,9-dibutylfluoren-2-yl)-2-(7-bromo-9,9-dibutylfluoren-2-yl)-isoindole-1-carboxamide, and N-[7-bromo-9,9-bis(2-ethylhexyl)-fluoren-2-yl]-2-[7-bromo-9,9-bis(2-ethylhexyl)-fluoren-2-yl]-isoindole -1-carboxamide was carried out by a three-component reaction of ortho-phthalaldehyde with the corresponding amine and isocyanide partners. The Ni(0) mediated polymerization reactions of the obtained monomers gave the corresponding mixture of oligomers from two up to twelve repeat units. The optical properties were also studied and it was found that the phenylene-containing oligomer emitted green light in dichloromethane solution, while both difluorene-containing oligomers, under the same conditions, proved to be blue light-emitters with good quantum efficiency.     

Substituent effect of fluorine atom on benzothiadiazole bridging unit in dye sensitized solar cells

Dye sensitized solar cells performances using two organic dyes with fluorinated-benzothiadiazole spacer, 3-{5-[7-(5-{4-[Bis(9,9-dimethyl-9H-fluoren-2-yl)-amino]-5-fluoro-phenyl}thiophen-2-yl)benzo-[1,2,5]thiadiazol-4-yl]thiophen-2-yl}-2-cyano acrylic acid (JK-311) and 3-{5-[7-(5-{4-[Bis(9,9-dimethyl-9H-fluoren-2-yl)-amino]-5,6-difluorophe-nyl}thiophen-2-yl)benzo-[1,2,5]thiadiazol-4-yl]thiophen-2-yl}-2-cyano acrylic acid (JK-312), were systematically investigated by solar simulation equipment, stepped light-induced transient measurements of photocurrent and voltage, and electrochemical impedance spectroscopy. To investigate substituent effect of fluorine atom on benzothiadiazole, molecular orbital calculations of two dyes using a time dependent density functional theory model with B3LYP/3-31G* were also carried out. JK-312 showed a unique electronic transition from HOMO-1 to LUMO. Short circuit current and open-circuit voltage in DSSCs performances were increased by the introduction of fluorine atom into spacer segment, compared to fluorine-free dyes.     

Syntheses and Characterization of 4-Octyloxybenzyl Substituted Diketopyrrolopyrrole-based Red Emitting Copolymers with Low Turn-on Voltage

Two novel diketopyrrolopyrrole-based alternating copolymers, poly(2,7-(9,9-diethyl)-fluorenylvinylene-alt-2,5-bis(4′-octyloxyphe- nylmethyl)-3,6-bis(4-vinylenephenyl)pyrrolo[3,4-c]pyrrole-1,4-dione) (P1) and poly(1,4-(2,5-dioctyl- oxy)-phenylenevinylene-alt-2,5-bis(4′-octyloxyphenylmethyl)-3,6-bis(4-vinylenephenyl)pyrrolo[3,4-c]pyrrole-1,4-dione) (P2) were synthesized through Wittig polycondensation in good yields. P1 and P2 were characterized by NMR, FT-IR, UV-Vis, photoluminescence (PL) and electroluminescence (EL). EL devices with ITO/PEDOT/polymer/CsF/Al exhibited red-emitting light with the maximum EL wavelength at 620 nm and 682 nm. The results show that PL quantum yield of the polymers in thin film can be improved through N-alkylation of diketopyrrolopyrrole (DPP) with bulky substituent. EL performance of P2 was better than P1, which might be due to 1,4-dioctyloxybenzene of P2 enhancing the hole-transporting to make more charge balance. EL devices of P1 and P2 possessed low turn on voltage (2.4 V and 2.1 V, respectively), which was an advantage for PLED.     

Reactions of 3-alkylsulfanyl-2-arylazo-3-(1-azacycloalk-1-yl)acrylonitriles with maleimide

Reactions of 2-arylazo-3-(1-azacycloalk-1-yl)-3-methylsulfanylacrylonitriles with male-imide in benzene gave octahydropyrrolo[3,4-a]pyrrolizines 2a–c, decahydro-2,7a-diaza-cyclopenta[a]indene 2e, and decahydro-5-oxa-2,7a-diazacyclopenta[a]indene 2f as a result of 1,3-dipolar cycloaddition. In a similar reaction with 3-allylsulfanyl-2-arylazo-3-(1-azacycloalk-1-yl)acrylonitriles 3, dipolar cycloaddition and intramolecular cyclization competed to give a mixture of compounds 2 (major products) and 1,4,6,7,8,8a-hexahydropyrrolo[2,1-c]-1,2,4-triazines 4b–d, 1,6,7,8,9,9a-hexahydro-4H-pyrido[2,1-c]-1,2,4-triazine 4e, and 1,4,6,7,9,9a-hexahydro-1,4-oxazino[3,4-c]-1,2,4-triazine 4f (minor products).     

Tuning the electronic structures and optical properties of fluorene-based donor–acceptor copolymers by changing the acceptors: a theoretical study

Five fluorene-based conjugated copolymers were studied to explore the effect of acceptor on the electronic and optical properties. Their ground-state, excited-state electronic structures and the tunable optical properties were theoretically investigated using density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. The acceptors including quinoxaline (Q), 2,1,3-benzothiadiazole (BT), thieno[3,4-b]pyrazine (TP), 2,1,3-benzooxadiazole (BO), and pyridopyrazine (PP) can significantly influence the copolymers’ electronic structures, molecular orbitals, geometric conformations, and optical properties. Calculations were made on systems containing one, two, three, and four oligomers in the neutral, cationic, and anionic structures, which can be extrapolated to infinite chain length polymers. The result indicated that the sequence of the band gap was on the reverse trend of emission wavelength. The strong electron-withdrawing strength of TP unit and coplanar backbone in poly[2,7-(9,9′-dihexylfluorene)-alt-2,3-dimethyl-5,7-dithien-2-yl-thieno[3,4-b] pyrazine] resulted in the enhanced degree of intramolecular charge transfer (ICT) and lowest band gap. The contribution of acceptors to IP was also found to follow the sequence of TP < Q < PP < BT < BO. The absorption and emission spectra exhibited red-shift with increasing the conjugation lengths. The present study suggested that the electronic and optical properties of donor–acceptor conjugated copolymers were affected by the acceptor structure.     

Incorporation of fluorene‐based emitting polymers into silica

Novel polyfluorene copolymers with pendant hydroxyl groups, poly[2,7‐(9,9‐dihexylfluorene)‐2,7‐(9,9‐bis(6‐hydroxyhexyl)fluorene)‐co‐2,7‐(9,9‐dihexylfluorene)‐1,4‐phenylene] (PFP‐OH) and poly[2,7‐(9,9‐dihexylfluorene)‐2,7‐(9,9‐bis(6‐hydroxyhexyl)fluorene)‐co‐2,7‐(9,9‐dihexylfluorene)‐4,7‐(2,1,3‐benzothiadiazole)] (PFBT‐OH) were prepared. Acid‐catalyzed polycondensations of tetraethoxysilane were carried out in the presence of these polymers to obtain homogeneous hybrids. Photoluminescence spectra of these hybrids suggested the polymers were immobilized in silica matrix retaining their π‐conjugated structures. Further, hybrids of coat film were prepared utilizing perhydropolysilazane as a silica precursor. Their optical properties were examined. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis of New Heterocyclic Systems on the Basis of 7-Benzyl-3-chloro-1-(morpholin-4-yl)-5,6,7,8-tetrahydro-2,7-naphthiridine-4-carbonitrile

Methods have been developed for the synthesis of new 8-amino-3-benzyl-5-(morpholin-4-yl)-1,2,3,4-tetrahydropyrimido[4′,5′: 4,5]thieno[2,3-c][2,7]naphthyridine starting from 7-benzyl-3-chloro-1-(morpholin-4-yl)-5,6,7,8-tetrahydro-2,7-naphthyridine-4-carbonitrile. 8-Hydrazinyl-3-benzyl-5-(morpholin-4-yl)-1,2,3,4-tetrahydropyrimido[4′,5′: 4,5]thieno[2,3-c][2,7]naphthyridine has been converted to isomeric pentacyclic structures with a triazole ring fused through the [c] side of the pyrimidine ring, and their Dimroth rearrangement has been accomplished in both acidic and basic media. New heterocyclic systems containing pyrrolo[1,2-a]pyrimidinone and pyrimido[1,2-a]azepinone fragments were obtained on the basis of the thieno-[2,3-c][2,7]naphthyridine derivative.     

2,7-萘二磺酸阴离子导向五元瓜环基超分子自组装体的制备及其荧光检测性能

通过引入2,7-萘二磺酸(2,7-NDA^2-)阴离子作为结构导向剂,与五元瓜环(Q[5])和过渡金属离子(Co²⁺、Ni²⁺、Zn²⁺、Cd²⁺)在水热条件下制备了4种新颖的Q[5]基超分子自组装体(Q[5]-SA),即{[M (H₂O)₄(Q[5])]·(NDA)}·xH₂O (M=Co (1)、Ni (2)、Zn (3))和{[Cd₂Cl₂(H₂O)₄(Q[5])]·(NDA)}·13H₂O (4)。单晶X射线衍射测试结果表明,自组装体1~3同构,其中Q[5]仅一端的部分端口羰基氧原子与金属离子配位形成简单配合物;而4中Q[5]的2个端口均与金属离子Cd²⁺配位形成了一维配位链。在自组装体1~4中,配体2,7-H₂NDA均全脱质子,形成2,7-NDA^2-阴离子平衡体系电荷,但均未能与金属离子配位,而在2,7-NDA^2-阴离子与Q[5]外壁之间的瓜环外壁作用下进一步形成三维超分子结构。此外,还研究了自组装体1和4的荧光传感性能,结果表明它们都能够作为抗生素诺氟沙星(NFX)的比率型荧光探针。     

A two-dimension medium band gap conjugated polymer based on 5,10-bis(alkylthien-2-yl)dithieno[3,2-d:3′,2′-d′]benzo[1,2-b:4,5-b′]dithiophene: Synthesis and photovoltaic application

A two-dimension medium band gap copolymer poly{5,10-bis(4,5-didecylthien-2-yl)dithieno[2,3-d:2′,3′-d′]benzo[1,2-b:4,5-b′]dithiophene-2,7-diyl-alt-2,5-di(3-octylthien-2-yl) thiophen-5,5′-diyl}, named as PDTBDT-T-3T, was prepared by the palladium-catalyzed Stille cross coupling reaction and characterized. The resulting polymer exhibits good solubility in common organic solvents, excellent thermal stability, and extensive light absorption from 300 nm to 650 nm with an optical band gap of 1.92 eV, the highest occupied molecular orbital (HOMO) level of ?5.03 eV and the hole mobility up to 1.92 × 10^?4 cm²·V^?1·s^?1. The power conversion efficiencies (PCEs) of 2.02%–3.19% have been achieved in the traditional PVCs for the copolymer. It should be noted that the PCEs of 4.2% for the inverted PVCs from the copolymer with PFN (poly[(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctyl- fluorene)]) as cathode modifying interlayer, were similar with the PCEs of 4.39% for the inverted PVCs from P3HT:PC₇₁BM at the same condition. These results indicated that the copolymer could be used as potential candidate for P3HT.     

螺二芴富勒烯吡咯烷衍生物的合成及电化学和光限幅性能

设计合成了3种新颖的螺二芴键联富勒烯(C60/C70)吡咯烷衍生物,其结构通过IR,1HNMR,13CNMR和MALDI-TOF进行确证,其电化学性质用循环伏安法进行研究.结果表明,C70衍生物6的还原电位较C60衍生物7分别向负电势移动0.1,0.12和0.01V.同时,使用纳秒和飞秒激光分别研究了化合物6,7和8的光限幅性能,其光限幅阈值分别为15.3,23.3和13.7J/cm2,表明这些材料具有优异的光限幅性能.     

Synthesis of novel spiro[indole-3,3′-pyrrolidin]-2(1H)-ones

Diastereoselective [3+2] cycloaddition of azomethine ylide to 1,3-dimethyl-6-(2-oxo-1,2-dihydro-3H-indol-3-ylidene)-3a,9a-diphenyl-3,3a,9,9a-tetrahydroimidazo[4,5-e]thiazolo[3,2-b]-[1,2,4]triazine-2,7(1H,6H)-dione yields hitherto unknown 1,1′,3-trimethyl-3a,9a-diphenyl-3,3a,9,9a-tetrahydrodispiro(imidazo[4,5-e]thiazolo[3,2-b][1,2,4]triazine-6,3′-pyrrolidine-4′,3″-indole)-2,2″,7(1H,1″H)-triones.     

Synthesen und Eigenschaften ethinylierter und trimethylsilylethinylierter Molekülsysteme mit 1,6-Methano[10]annulen-Partialstruktur

2-Trimethylsilylethinylated 1,6-methano[10]annulene1 a was obtained by reaction of 2-bromo-1,6-methano[10]annulene with trimethylsilylacetylene in the presence of bis-(triphenylphosphin-)-Pd (II) chloride and Cu(I) and also by reaction of 1,1-diiodo-2-(1,6-methano[10]annulene-2-yl)-ethene (2) withn-buthyl-lithium followed by hydrolysis.1 a reacts with 2N NaOH to 2-ethinyl-1,6-methano[10]annulene (1 b). 2,7- and 2,10-dibromo-1,6-methano[10]annulene can be substituted to give the trimethylsilylethinylated compounds3 a–6 a, which then can be transformed with 2N NaOH into the desilylated products3 b–5 b.

Wolfgang Kraus, Stuttgart-Hohenheim, mit den besten Wünschen in Freundschaft zum 60. Geburtstag gewidmet     

基于蓝黄磷光二元互补色的高效聚合物白光器件

研究了基于互补色的高效聚合物白光器件,双色材料包括蓝绿光材料双(4,6-二氟苯基吡啶-N,C2)吡啶甲酰合铱(Firpic)和黄光材料三[3-(2,6-二甲基苯氧基)-6-(2-噻吩基)-哒嗪]铱(Fs-1),器件结构为ITO/PEDOT(40 nm)/PVK:OXD-7:Firpic:Fs-1(80 nm)/Ba(4 nm)/Al(120 nm).当发光层材料PVK∶OXD-7∶Firpic∶Fs-1质量比为63∶27∶10∶0.25时,用溶液加工方法得到高效白光器件,此时CIE色坐标为(0.30,0.39),最大电流效率为10.8 cd.A-1,亮度可达到4200 cd.m-2.在此基础上,引入水溶性电子注入材料聚[9,9-二(3′-N,N-二甲基胺基丙基-2,7-芴-2,7-交-(9,9-二辛基芴)](PFN)修饰阴极界面,使载流子注入和传输更平衡,当阴极为PFN(20 nm)/Al(120 nm)时,电流效率获得显著改善,达到13.1 cd.A-1,此时电流密度为4.9 mA.cm-2,亮度可达到6096 cd.m-2,白光器件的色坐标为(0.33,0.39),同时发光光谱稳定.另外通过电致发光(EL)、光致发光(PL)光谱及能级结构图分析了载流子俘获和能量转移在发光中的作用.     

2，7-萘二磺酸导向构筑的五元瓜环-碱金属及碱土金属基超分子自组装体及其溶剂识别

以2,7-萘二磺酸（2,7-H₂NDA）作为结构导向剂,与五元瓜环（Q[5]）和碱金属、碱土离子（K⁺、Rb⁺、Mg²⁺、Ca²⁺）在水热条件下制备出了4种新颖的Q[5]基超分子自组装体[K₂（H₂O）₄（Q[5]）]（2,7-NDA）·4H₂O （1）、[Rb₂（H₂O）₅（Q[5]）]（2,7-NDA）·3H₂O （2）、[Mg （H₂O）₄（Q[5]）]（2,7-NDA）·8H₂O （3）和[Ca （H₂O）₄（Q[5]）]（2,7-NDA）·10H₂O （4）。单晶X射线衍射测试结果表明,自组装体1和2具有相同的结构： Q[5]分子与金属离子配位形成的是“分子胶囊”;而在3中Q[5]与Mg²⁺配位形成的是1：1型简单配合物结构;在自组装体4中,Q[5]与Ca²⁺配位形成的是一维Q[5]-Ca²⁺配位聚合物链结构。这些结构中2,7-NDA^2-阴离子平衡了体系电荷,且通过其与瓜环外壁之间的弱相互作用,促进自组装体最终构筑成三维超分子结构。此外,还研究了自组装体4的溶剂识别荧光传感性能,结果表明其能够作为有机溶剂丙酮和DMF的猝灭型荧光探针。     

2,7-萘二磺酸阴离子导向五元瓜环基超分子自组装体的制备及其荧光检测性能

通过引入2,7-萘二磺酸(2,7-NDA^2-)阴离子作为结构导向剂,与五元瓜环(Q[5])和过渡金属离子(Co²⁺、Ni²⁺、Zn²⁺、Cd²⁺)在水热条件下制备了4种新颖的Q[5]基超分子自组装体(Q[5]-SA),即{[M(H₂O)4(Q[5])]·(NDA)}·x H₂O(M=Co (1)、Ni (2)、Zn (3))和{[Cd2Cl2(H₂O)4(Q[5])]·(NDA)}·13H₂O (4)。单晶X射线衍射测试结果表明,自组装体1～3同构,其中Q[5]仅一端的部分端口羰基氧原子与金属离子配位形成简单配合物;而4中Q[5]的2个端口均与金属离子Cd²⁺配位形成了一维配位链。在自组装体1～4中,配体2,7-H2NDA均全脱质子,形成2,7-NDA2-阴离子平衡体系电荷,但均未能与金属离子配位,而在2,7-NDA2-阴离子与Q[5]外壁之间的瓜环外壁作用下进一步形成...     

Solvent-Free Synthesis of Novel Highly Functionalized Dihydroanthra[1,2-b]furan-6,11-dione Derivatives

A convenient and environmentally friendly solvent-free procedure has been developed to react 1,5-dihydroxyanthraquinone with dialkyl acetylenedicarboxylates in the presence of triphenylphosphine in one pot to afford novel dialkyl (E)-2-{1,5-dihydroxy-6-[3-methoxy-1-(methoxycarbonyl)-3-oxo-2-(triphenyl-λ ⁵-phosphanylidene)propyl]-9,10-dioxo-9,10-dihydro-2-anthracenyl}-2-butanedioate 3a–c. As a result of intramolecular nucleophilic attack at 90 °C, novel dialkyl (E)-2–{2,7-dihydroxy-3-[2-methoxy-2-oxo-1-(triphenyl-λ ⁵ phosphanylidene)ethyl]-6,11-dioxo-6,11-dihydroanthra[1,2-b]furan-8-yl}-2-butanedioates 4a–c were produced in good yield.     

Efficient Synthesis of Substances Related to Cinacalcet Hydrochloride via Heck Coupling

Efficient synthetic methods to process substances related to cinacalcet hydrochloride 1, generated during the preparation, were described. The compounds were identified as [1-(7,8-dihydro-naphthalen-1-yl)-ethyl]-[3-(3-trifluoromethyl-phenyl)-propyl]-amine hydrochloride 2,[1-(5,6,7,8-tetrahydro-naphthalen-1-yl)-ethyl]-[3-(3-trifluoromethyl-phenyl)-propyl]-amine hydrochloride 3 and [1-(naphthalen-2-yl)-ethyl]-[3-(3-trifluoromethyl-phenyl)-propyl]-amine hydrochloride 4. All were prepared from commercially available materials in several linear steps and characterized by their respective spectral data.     

Carbazole-modified blue light-emitting copolymers with the backbones integrated by diphenyloxadiazole,fluorene, and triphenylamine

Two new blue light-emitting polymers, poly{[2,5-bis(4-phenylene)-1,3,4-oxadiazole]-[9,9-dihexylfluorene-2,7-diyl]-[N-(4-(9H-carbazol-9-yl)phenyl)-N,N-bis(p-phenylene)aniline]} (POFPA) and poly{[2,5-bis(4-phenylene)-1,3,4-oxadiazole]-[9,9-dihexylfluorene-2,7-diyl]-[4-(3,6-(di-9H-carbazol-9-yl)-9H-carbazol-9-yl)-N,N-bis(p-phenylene)-aniline]} (POFCPA), were synthesized by Suzuki coupling reactions. By GPC analysis against a linear polystyrene standard POFPA and POFCPA were found to have M_n of 1.68 × 10⁴ and 3.70 × 10³, respectively. In contrast to POFPA, the main absorption peak of POFCPA in dilute toluene solution was blue-shifted by Δλ = 26 nm owing to its backbone of relatively shorter π-conjugation length and more carbazole units in side chain. The absolute fluorescence quantum yield (Φ_f) of POFCPA in dilute toluene solution was determined as 73%, much higher than that of POFPA (Φ_f ≈ 58.9%) measured under the same conditions. An electroluminescence device based on POFCPA displays a stable blue emission having color coordinates of (0.15, 0.20), a maximum brightness of 4762 cd/m², and a maximum current efficiency of 1.79 cd/A. By using this polymer as the host material doped with 1 wt.% 4,4′-bis[2-(4-(N,N-diphenylamino)phenyl)vinyl]biphenyl, the achieved highest brightness, maximum current efficiency and maximum power efficiency are 13,613 cd/m², 3.38 cd/A, and1.84 lm/W, respectively.