Synthesis of novel organosilicon polymers and approach to high functionality materials

1.合成了聚（二硅亚基）低聚苯撑和聚（二硅亚基）低聚噻吩撑，并研究了它们的光化学、导电和热性能。有趣的是，这些聚合物的光活性随着在二硅亚基单元之间的亚苯基和亚噻吩基单元的数目的增加而降低。这些结果与简化模型聚合物的晶体轨道计算结果一致，即HOCO和LUCO都随着π电子体系的膨胀而从σ型转变为π型。2.合成了含吡啶亚基的聚合物。这些聚合物具有很高的光活性，并通过掺杂I_2和FeCl_3而变得导电。3.我们发现，在铑催化剂存在下，聚硅撑二乙炔的区域特异性1，2-硅氢化反应提供了一条制备支化聚合物的方便途径。这些聚合物可溶于普通有机溶剂，可用光谱分析法进行全面表征。我们还制备了一些支化低聚硅烷作为支化聚硅烷的模型，并研究了它们的光化学性质。4.通过开环聚合合成含硅杂环的聚合物，研究了含硅氢聚合物的合成、反应和热性能，以及通过电化学形成硅键制备聚合物。

1.Poly [(disilanylene) oligophenylenes] and poly [(disilanylene) oligothienylenes] were synthesized and their photochemical, conducting, and thermal properties were investigated. Interstingly, the photoactivities of these polymers decrease with increasing the number of phenylene and thienylene units betweed disilanylene units. These results are in accordance with the results of crystal orbital calculations on simplyfied model polymers, which predict that both HOCO and LUCO interchange from sigma-type to pi-type with the expansion of the pi-electron system.2.Polymers having a pyridylene unit were synthesized. These polymers are highly photoactive and become conducting upon doping with I_2 and FeCl_3.3.We found that regiospecific 1,2-hydrosilylation of poly (silylenediethynylene) in the presence of a rhodium catalyst offers a convenient route to branched polymers. These polymers are soluble in common organic solvents and can be wholly characteryzed by spectrometric analysis. We also prepared some branched oligosilanes as models of branched polysilanes and investigated their photochemical properties.4.Synthesis of polymers containing a silole skeletal by ring-openeing polymerization of the respective cyclic compounds, synthesis, reactions, and thermal properties of Si-H-containing polymers, and preparation of polymers by electrochemical Si-Si bond formation were also investigated.