Synthesis and Application of New Conductive Compounds Bearing Ferrocene and S-Heterocycles.

本论文主要研究了两个方面的问题：（1）以四硫富瓦烯（TTFs）为配体的二茂铁导电电荷转移（CT）配合物的合成;（2）含二茂铁噻吩低聚物的合成。(1)以邻氨基苯甲酸为原料合成了2-二甲氧基氧膦基-1，3-苯并二硫杂环戊烯，然后用Wittig-Horner法，在-78 ~100 ℃，正丁基锂存在下，与二茂铁酮（或苯酮）在干燥的THF中反应，得到给体化合物。用此方法合成了含二茂铁基的含甲基、苯基、杂环的TTFs的新型给体化合物。在CH_2Cl_2中，给体化合物与有机受体TCNQ或TCNQF_4在回流温度下反应，得到CT配合物。电导率测量显示当<-1>1，1 '-二取代的二茂铁-TTFs-TCNQ化合物的情况下具有显著的电导率（σ = 0.26S cm-3）。（2）利用钯催化反应合成了以三键或双键与二茂铁环连接的3-取代噻吩衍生物。以2-溴噻吩和噻吩硫番为原料，在钯催化剂作用下进行了杯合反应。得到了低聚物，但分离不成功。电化学性能也检查了这些化合物。

Two themes were investigated, (1)synthesis of new donor compounds which have tetrathiafulvalenes (TTFs) bearing ferrocene ring derived to conducting charge transfer (CT) complex ; (2)synthesis of thiophene oligomers bearing ferrocene ring.(1): As an example, 2-dimethoxy-phosphinyl-1,3-benzodithiole was prepared from anthranilic acid, then treatment of this phosphonate ester with ferrocenyl ketones (or phenyl keton as comparison) using the Wittig-Horner method in the presence of n-BuLi at-78 to 〜0℃ in dry THE afforded the donor compounds. New donor compounds which have ferrocene-TTFs bearing methyl, phenyl, hetero ring were synthesized by this way. The CT complexes were obtained from the reaction of the donor compounds with the well-known organic acceptor TCNQ or TCNQF_4 in CH_2Cl_2 at reflux temperature. The electrical conductivity measurement showed a substantial conductivity (σ = 0.26 S cm^<-1> ) when the case of 1,1'-disubstituted Ferrocene-TTFs-TCNQ compound.(2)3-Substituted thiophene derivatives which bind to ferrocene ring by triple or double bond were synthesized using palladium catalytic reaction. The cuppling reaction of 2-bromothiophene and thiophane was carried out using palladium catalyst. Oligomer compounds were obtained, but separation were not succeeded. Electrochemical properties were also examined for these compounds.