PREPARATION AND PROPERTIES OF NOVEL POLYTHIOPHENES CONTAINING 1,3-DITHIOL-2-YLIDENE MOIETIES
PREPARATION AND PROPERTIES OF NOVEL POLYTHIOPHENES CONTAINING 1,3-DITHIOL-2-YLIDENE MOIETIES
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DOI：
10.1021/jo00081a026
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发表时间：
1994-01-28
影响因子：
3.6
通讯作者：
YAMASHITA, Y
中科院分区：
文献类型：
--
作者：
KOZAKI, M;TANAKA, S;YAMASHITA, Y
通过Wittig-Horner或Wittig反应合成了4-（1，3-二硫醇-2-亚基）-4H-环戊二烯并[2，1-B; 3，4-b ']二噻吩1和7-（1，3-二硫醇-2-亚基）-7H-环戊二烯并[1，2-B; 4，3-b']二噻吩2。母体化合物1a和2a的X-射线结构分析表明，这两个分子都具有平面结构，分子间存在短的链节。S接触，和2a另外具有短的分子内S…S接触。由于1，3-二硫杂环戊烯骨架，它们具有低的氧化电位和在长波长区域的吸收。1和2的电化学氧化得到相应的聚合物3和4，其具有低氧化电位。3和4的电化学去掺杂膜在电子光谱中分别在610-690 nm和420-590 nm处有带间吸收。3和4的一些膜在掺杂下表现出高电导率，例如3c。（PF6-）（x）33 S cm（-1）和3e.（BF4-）（x），52 S cm（-1）。合成了含有线性烷基链的衍生物3f-h，以提高其在有机溶剂中的溶解度，并发现其在THF和氯仿中有一定的溶解度。去掺杂的3g在1H-1 NMR谱中显示宽峰，归属于烷基质子。MNDO-PM 3计算表明，1a和2a的二聚体和三聚体中相邻单体片段之间的扭转角约为30度。INDO/1计算结果表明，1a衍生的低聚物比2a衍生的低聚物具有更大的共轭体系。
4-(1,3-Dithiol-2-ylidene)-4H-cyclopenta[2,1-b;3,4-b']dithiophenes 1 and 7-(1,3-dithiol-2-ylidene)-7H-cyclopenta[l,2-b;4,3-b'] dithiophenes 2 were prepared by Wittig-Horner or Wittig reactions. The X-ray structural analyses of the parent compounds 1a and 2a reveal that both molecules have planar structures with short intermolecular S...S contacts, and 2a additionally has short intramolecular S...S contacts. They have low oxidation potentials and absorptions in a long wavelength region due to the 1,3-dithiole skeleton. Electrochemical oxidation of 1 and 2 afforded the corresponding polymers 3 and 4, which have low oxidation potentials. Electrochemically dedoped films of 3 and 4 have interband absorptions at 610-690 nn and 420-590 nm, respectively, in their electronic spectre. Some films of 3 and 4 exhibited high electrical conductivities with doping, for instance, 3c.(PF6-)(x) 33 S cm(-1) and 3e.(BF4-)(x), 52 S cm(-1). Derivatives 3f-h, containing linear alkyl chains, were synthesized in order to enhance solubilities in organic solvents and were found to be somewhat soluble in THF and chloroform. Dedoped 3g showed broad peaks in the H-1 NMR spectrum, assigned to the alkyl protons. MNDO-PM3 calculations showed that the torsion angles between the neighbor monomer fragments in the dimers and trimers of 1a and 2a are about 30 degrees. However, the oligomers derived from 1a have more extended conjugated systems than those from 2a, which was indicated by INDO/1 calculations.