Blue electroluminescence from 3,6‐silafluorene‐based copolymers

Poly(3,6‐silafluorene) is a typical wide band‐gap conjugated polymer with ultraviolet light emission. The blue electroluminescence from the 3,6‐silafluorene‐based copolymers via intrachain energy transfer was reported in this study. The monomer containing vinylene, anthracene, and tri‐arylamine moieties incorporated into the poly(3,6‐silafluorene) backbone can form efficient deep‐blue emitting copolymers with EL efficiency of 1.1–1.9%. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3286–3295, 2009     

双室聚丙烯低温反应瓶的设计制造及在硅芴合成中的应用

设计制造了瓶底有一大一小2个室的聚丙烯（PP）塑料反应瓶,将其用于活泼的金属有机反应中硅芴的合成。 首先将制备的2,2′-二锂基联苯（2）转移到小室中,然后将SiCl4溶液注入大室内,再将反应瓶倾斜,使得化合物2的溶液分次进入大室进行反应,保证反应在SiCl4充分过量条件下进行,可大大降低螺硅芴（4）副反应产物的生成,使9,9-苯基硅芴的产率由20%提高至35%~40%,SiCl4的用量降至4倍摩尔量,从而也降低了产物后处理中柱分离的处理量。     

Syntheses,electrochemical and spectroelectrochemical characterization of benzothiadiazole and benzoselenadiazole based random copolymers

Three novel donor-acceptor-donor type random copolymers based on benzothiadiazole (BTh) and benzoselenadiazole (BSe) were synthesized via Pd (0) catalyzed Suzuki polycondensation reaction. The two acceptor units were coupled with electron rich moieties which are carbazole (CZ), fluorene (FL) and silafluorene (SiFL). Monomers were characterized using ¹H and ¹³C-NMR spectroscopy. The number and weight average molecular weights of the polymers were calculated using gel permeation chromatography (GPC). All three polymers were electrochemically and spectroelectrochemically characterized. PBThBSeCZ, PBThBSeFL and PBThBSeSiFL showed only p-dopable character and their doping/dedoping potentials were determined as 1.4 V/1.2 V, 1.53 V/1.27 V and 1.8 V/1.3 V, respectively. Corresponding HOMO energy levels were calculated as ?5.85 eV, ?6.05 eV and ?6.15 eV whereas LUMO energy levels were found to be ?3.67 eV, ?3.84 eV and ?3.77 eV, respectively. PBThBSeCZ had lower HOMO level and band gap than PBThBSeFL and PBThBSeSiFL due to its increased electron donating capability of nitrogen atom in carbazole unit.     

新型噻咯共轭聚合物的合成及其光伏性能

噻咯(silole)是一类含硅的五元环二烯, 具有很好的电子亲和力、独特的聚集态诱导发光性质和优良的电致发光性能. 研究者发现将噻咯结构单元引入分子主链中, 能够获得具有特殊光电性能的聚合物材料. 本工作合成两种2,5位为二噻吩苯并噻二唑的新型噻咯单体, 通过与芴或硅芴双硼酸酯Suzuki偶联聚合, 制备四种主链型D-A(推-拉电子结构)共聚物PF-HSTBT, PF-HOSTBT, PSiF-HSTBT和PSiF-HOSTBT. 研究表明, 四种聚合物具有较好的吸收, 光学带隙均小于1.71 eV. 电化学分析测得四种聚合物的HOMO能级均小于-5.29 eV, 通过光学带隙计算得LUMO能级均高于-3.61 eV. 以四种聚合物分别作为电子给体材料, PC₆₁BM为受体材料, 制备了聚合物太阳能电池器件(PSCs). 由于聚合物PF-HOSTBT、PSiF-HOSTBT中的己氧基空间位阻较大, 分子平面规整性较差, 其最高光电转换效率分别为0.62%、0.83%; 而己基的空间位阻较小, 分子堆积紧密, 聚合物PF-HSTBT, PSiF-HSTBT的光伏性能较优, PSCs的最高光电转换效率分别为1.18%, 1.2%.     

Ring‐Shaped Silafluorene Derivatives as Efficient Solid‐State UV‐Fluorophores: Synthesis,Characterization, and Photoluminescent Properties

Four ring‐shaped silafluorene‐containing compounds ( 1 – 4 ) were synthesized and characterized as potentially promising monomers for fluorescent polymers. Their optical properties in solution and solid state (thin film and powder) were studied. These compounds have low quantum yields in solution (Φ_fl=0.13‐0.15) with fluorescence maxima at about 355 nm, but high quantum yields in the solid state (powder, Φ_fl=0.35‐0.54) with fluorescence maxima at about 377 and 488 nm. Influence of the substituents and the number of silafluorene units in 1 – 4 on their optical properties was investigated. Extensive study of the X‐ray crystal structures of 1 – 4 was undertaken to analyze and qualitatively estimate the role, extent, and influence of silafluorene moieties’ interactions on solid‐state fluorescent properties. Excited state UV/Vis and theoretical molecular orbital (MO) calculations were performed to explore possible fluorescence mechanisms and differences in quantum yields among these compounds.     

High‐efficiency blue light‐emitting polymers based on 3,6‐silafluorene and 2,7‐silafluorene

A novel blue‐emitting polymer based on 3,6‐silafluorene and 2,7‐silafluorene was synthesized via the Suzuki polycondensation. The resulting polymers are readily soluble in common organic solvents, such as toluene, xylene, THF, and chloroform. The thermal, electrochemical, photophysical, and electroluminescence properties of the resulting polymers were investigated. The device fabricated from the copolymer with a configuration of ITO/PEDOT:PSS/PVK/polymer/Ba/Al exhibited an external quantum efficiency of 1.95%, a luminous efficiency of 1.69 cd A^?1 and a maximal brightness of 6000 cd m^?2. It has been found that the incorporation of the 3,6‐silafluorene unit into the poly(2,7‐silafluorene) main chain can not only improve the color purity of the devices from the resulting copolymer but also enhance its device efficiency. Moreover, no undesired long‐wavelength green emission was observed in the PL spectra of P36‐27SiF90 compared to that of PFO with a dominating emission at 500–600 nm after thermal annealing at 200 °C for 8 h. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4941–4949, 2007     

硅芴类化合物的合成及应用研究进展

近年来,芴类结构9-位为硅桥联的硅芴类化合物以其独特的电子结构和光电性能受到研究者们越来越多的关注,这类化合物在有机发光二极管(OLED)、聚合物太阳能电池(PSC)、有机场效应管(OFET)等光电功能材料领域有广泛的应用前景。本文主要对硅芴类化合物的合成方法、结构修饰、性能及应用研究的最新进展进行了综述。     

Silafluorene‐based polymers for electrochromic and polymer solar cell applications

In this study, four novel silafluorene (SiF) and benzotriazole (Btz) bearing conjugated polymers are synthesized. In the context of electrochemical and optical studies, these polymers are promising materials both for electrochromic device (ECD) and polymer solar cell (PSC) applications. All of the polymers are ambipolar (both p‐ and n‐dopable) and multichromic. Electrochemistry experiments indicate that incorporation of selenophene instead of thiophene unit increases the HOMO energy level of the polymers. Power conversion efficiency of the PSCs reached 1.75% for PTBTSiF, 1.55% for PSBSSiF, 2.57% for PBTBTSiF, and 1.82% for PBSBSSiF. The hole mobilities of the polymers are estimated through space charge limited current (SCLC) model. PBTBTSiF has the highest hole mobility as 2.44 × 10^?3 cm² V s^?1. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1541–1547