Synthesis,processing, and third-order nonlinear optical properties of benzobisthiazole polymers containing thiophene moieties

Benzobisthiazole polymers containing mono-, bi-, and terthiophene moieties were synthesized through polycondensation in polyphosphoric acid of 2,5-diamino-1,4-benzenedithiol dihydrochloride with thiophene-2,5-dicarboxylic acid, 2,2′-bithiophene-5,5′-dicarboxylic acid, and 2,2′:5′,2″-terthlophene-5,5″-dicarboxylic acid, or their corresponding diacid chlorides, respectively. Intrinsic viscosities of up to 8.1 dL/g (methanesulfonic acid, 30°C) were recorded. Polymer structures were verified by elemental analysis and spectroscopic comparison of the polymers with appropriate model compounds. Onset of breakdown under thermogravimetric analysis in air occurred in the 460–590°C range with the benzobisthiazole polymers containing a monothiophene linkage being the most stable. Films suitable for third-order optical susceptibility measurements could be prepared by extrusion techniques from the benzobisthiazole polymer containing a monothiophene linkage. Degenerate four wave mixing measurements on this film yielded a third order optical susceptibility χ⁽³⁾ of approximately 4.5 × 10^?10 esu. © 1993 John Wiley & Sons, Inc.     

二噻吩衍生物的合成及其线性、非线性光谱性质

合成了一系列二噻吩衍生物类有机合物：5，5'-二（对－N，N－二甲胺基苯乙 烯基）－2，2'－二噻吩（BMSBT）与5，5'－二（对－N，N－二乙胺基苯乙烯基）- 2,2'-二噻吩（BESBT），5,5'-二（对N－环丁胺基苯乙烯基）－2,2'－二噻吩（ BBSBT），5,5－二（对－N－咔唑基苯乙烯基）2-2'－二噻吩（BCSBT），并测定了 其吸收光谱、单光子荧光光谱和双光子荧光光谱。BMSBT，BESBT和BBSBT的单光子 荧光参数存在的很强的、规则的溶剂效应，表明其激发态的分子可能有较大的极性 。在800nm fs激光下测得BMSBT与BESBT在560nm附近（与单光子荧光发射峰波长接 近的位置）有较强的上转换荧光发射，上转换荧光强度与激发能量之间较好的平方 关系表明了双光子激发的机理，这种上转换荧光被称为双光子荧光。用以光子荧光 法测得BMSBT和BESBT的双光子吸收截面分别为54*10~(-50)(cm~4·s)/photon和 102*10~(-50)(cm~4·s)/photon。     

Distannylated Bithiophene Imide: Enabling High‐Performance n‐Type Polymer Semiconductors with an Acceptor–Acceptor Backbone

A distannylated electron‐deficient bithiophene imide (BTI‐Tin) monomer was synthesized and polymerized with imide‐functionalized co‐units to afford homopolymer PBTI and copolymer P(BTI‐BTI2), both featuring an acceptor–acceptor backbone with high molecular weight. Both polymers exhibited excellent unipolar n‐type character in transistors with electron mobility up to 2.60 cm² V^?1 s^?1. When applied as acceptor materials in all‐polymer solar cells, PBTI and P(BTI‐BTI2) achieved high power‐conversion efficiency (PCE) of 6.67 % and 8.61 %, respectively. The PCE (6.67 %) of polymer PBTI, synthesized from the distannylated monomer, is much higher than that (0.14 %) of the same polymer PBTI*, synthesized from typical dibrominated monomer. The 8.61 % PCE of copolymer P(BTI‐BTI2) is also higher than those (<1 %) of homopolymers synthesized from dibrominated monomers. The results demonstrate the success of BTI‐Tin for accessing n‐type polymers with greatly improved device performance.     

Synthesis,characterization, and photovoltaic properties of novel conjugated copolymers derived from phenothiazines

Two novel series of soluble alternating conjugated copolymers comprising 10‐alkylphenothiazine and bithiophene or 3‐pentylthieno[3,2‐b]thiophene moieties were synthesized using palladium‐catalyzed Suzuki coupling reaction. The structures of the polymers and their thermal, photophysical, electrochemical, and photovoltaic properties were characterized and investigated. The polymers exhibited good thermal stability with decomposition temperature in the region of 342–390 °C and their glass transition temperatures (T_g) ranging from 126 to 150 °C. All polymers demonstrate broad optical absorption in the region of 300–500 nm with efficient blue‐green light emission. They showed ambipolar redox properties with low HOMO levels around ?5.13 eV. Polymer solar cells were fabricated using blends of the copolymers and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) in a 1:1 weight ratio. The maximum power conversion efficiency (η = 0.24%) was measured for the poly[3,7‐ (10‐hexylphenothiazine)‐alt‐bithiophene] as donor under simulated sun light (1000 W/m²). Open circuit voltages of up to 0.8 V have been obtained. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5266–5276, 2007     

联二噻吩稠合的近红外BODIPY染料的合成与光谱性质

以叠氮乙酸乙酯和联二噻吩甲醛为原料,合成了联二噻吩并吡咯单体,之后在酸催化下与4-N,N-二甲基氨基苯甲醛缩合并与三氟化硼配位,得到一个新型的BODIPY染料SY。采用~1HNMR、质谱以及元素分析对其结构进行了表征。化合物SY在二氯甲烷中的最大吸收和发射波长分别为654和689nm;采用荧光光谱滴定方法研究了它对pH值的响应,酸性条件下N,N-二甲基苯氨基团发生质子化,抑制了光诱导电子转移对BODIPY母体的荧光淬灭,其溶液的荧光显著增强,染料SY可以作为近红外的pH值荧光探针。     

Two—photon Excited Fluorescence of Bithiophene Derivatives

Two new bithiophene derivatives named as 5,5‘‘-bis(p-N,N-dimethylaminostyryl)-2,2‘-bithiophene (BMSBT),and 5,5‘-bis(p-N,N-diethylaminostyryl)-2,2‘-bithiophene (BESBT) have been synthesized.Both compounds can emit strong single-photon excited fluorescence (SPEF) and two-photon excited fluorescence (TPEF) with the emission peaks around-560nm and with the lifetime of-1ns.     

Recent progress in lactam-based polymer semiconductors for organic electronic devices

Numerous polymer semiconductor materials with alternating electron donor–electron acceptor (D–A) structures have attracted immense attention because they exhibit excellent semiconductor performance and solution processability. These materials can be used for the fabrication of various lightweight and flexible electronic devices. In this review, we provide a brief overview of the structural features and important properties of lactams whose performance can be enhanced by introducing an acceptor in the design of D–A-type polymer semiconductor materials. The focus is on polymer semiconductor materials with lactams in their structures, such as diketopyrrolo[3,4-c]pyrrole, naphthalene diimide, isoindigo, 2,2-bithiophene-3,3-dicarboximide, and thieno[3,4-c]pyrrole-4,6-dione. The recent advances made in the field in the last 3 years are discussed. In addition, the application of polymers for the fabrication of organic electronic devices and the progress in the field are discussed.     

Synthesis and photovoltaic properties of copolymers based on bithiophene and bithiazole

Three simple structured D‐A copolymers, PBTBTz‐1 , PBTBTz‐2 , and PBTBTz‐3 , containing bithiophene (BT) donor unit and bithiazole (BTz) acceptor unit with different alkyl chain length were synthesized by the Pd‐catalyzed Stille‐coupling method. The copolymers were characterized by thermogravimetric analysis, UV–vis absorption, electrochemical cyclic voltammetry, and photovoltaic measurements. The results indicate that the introduction of BTz unit to the polythiophene main chain effectively decreases highest occupied molecular orbital levels of the copolymers and increases the open circuit voltage (V_oc) of polymer solar cells (PSCs) based on the copolymers as donor, and the alkyl chain length influences the photovoltaic properties of the polymers significantly. The PSCs based on PBTBTz‐2 and PBTBTz‐3 show higher V_oc up to 0.77 and 0.81 V, respectively. The power conversion efficiency of the PSC based on PBTBTz‐2 :PC₇₀BM = 1:1(w/w) reached 2.58% with short circuit current of 8.70 mA/cm², under the illumination of AM1.5, 100 mW/cm². © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Differential Pulse Techniques on Modified Conventional‐Size and Microelectrodes. Electroactivity of Poly[4,4′‐bis(butylsulfanyl)‐2,2′‐bithiophene] Coating Towards Dopamine and Ascorbic Acid Oxidation

Poly[4,4′‐bis(butylsulfanyl)‐2,2′‐bithiophene] modified conventional‐size and (ultra)microelectrodes are first investigated in acetonitrile and quasi‐neutral aqueous solution with respect to the repeatability of the responses obtained both in cyclic voltammetry and in differential pulse voltammetry. The reactivity towards ferrocene and hydroquinone, chosen as benchmark oxidizable substances in the two media, respectively, is considered. Comparison is made with the behavior of poly(3‐methylthiophene) as electrode coating, which is one of the most commonly used redox mediators in amperometric sensors based on coatings consisting of conducting polymers. The results confirm the appealing properties of poly[4,4′‐bis(butylsulfanyl)‐2,2′‐bithiophene], previously evidenced by us in different electrochemical studies: it exhibits particularly high stability and the characteristics of the current/potential curves obtained make it particularly suitable for analytical purposes. After performing these tests, the quantitative determination of dopamine by modified microelectrode is examined and the simultaneous voltammetric determination of ascorbic acid and dopamine is considered. The possibility of working profitably with a microelectrode at very low buffer‐supporting electrolyte concentration is ascertained.     

联噻吩桥联双三联吡啶的合成、质子化及其与金属离子的配位

以2,5-二溴噻吩为底物, 经醛基化、Kröhnke吡啶合成反应、Suzuki偶联三步制备了联噻吩桥联双三联吡啶 (BTTPY,总产率13%).通过紫外吸收及荧光光谱研究了其在酸性介质中的质子化效应, BTTPY在乙酸和三氟乙酸中的吸收及荧光光谱较非质子溶剂中均有明显红移.借助紫外吸收滴定法研究了其与过渡金属离子(Ni²⁺、Zn²⁺、Cd²⁺、Cu²⁺)的配位作用.结果表明BTTPY可与这些金属离子形成1:1的配合物,原子力显微镜 (AFM)图像显示, BTTPY与铬离子所形成的配位聚合物主要呈现一维堆积.