Synthesis of σ-π conjugated non-linear optical materials by olefin metathesis

σ-π杂化共轭分子是一种具有光学非线性和高透明度的新型有机材料。聚（硅-乙烯）是这些候选者之一。首次尝试用烯烃复分解法合成聚硅烯烃-乙烯。以Re_2O_7-Al_2O_3为催化剂，在温和反应条件下，由四乙烯基硅烷和二甲基乙烯基硅烷自分解和1,4-双（二甲基乙烯基硅基）苯合成了线型低聚物（二聚物~低聚物）。发现它们是高透明度的σ-π杂化共轭分子，但无法得到高透明度的低聚物和聚合物。光谱学研究表明，它们的光学非线性较弱。二茂铁是一种具有光学非线性的有趣化合物。在Grubbs和Schrock催化剂上，通过交叉复分解，尝试了两种体系具有不同功能基团的π共轭分子的选择性合成。(1)各种乙烯基芳烃和乙烯基异芳烃与1 -辛烯的交叉复合反应；(2)乙烯基二茂铁与一系列乙烯基芳烃的交叉复合反应。乙烯基二茂铁没有发生自我复分解，但有趣的是，在施罗克催化剂的存在下，交叉复分解继续产生高选择性（73- 100%）的异二聚体（交叉复分解产物）。提出了选择性异二聚体形成的机理。

σ-π hybrid conjugated molecules have been expected as new organic materials with optical non-linearities with high transparency. Poly (silylene-vinylene) s are one of these candidates.Syntheses of poly (silylene-vinylene) s by olefin metathesis were attempted for the first time. New compounds, oligo (silylene-vinylene) s (dimer〜oligomer) of linear type were synthesized by self-metathesis of tetravinylsilane and dimethyldlvinylsilane, and 1,4-bis(dimethylvinylsilyl) benzene using Re_2O_7-Al_2O_3 catalyst under mild reaction conditions. It was found they are σ-π hybrid conjugated molecules with high transparency, but higher oligomer and polymer could not be obtained. The spectroscopic studies revealed that their optical nonlinearities are weak.Ferrocene is known as one of interesting compounds with optical non-linearities.Novel selective synthesis of π -conjugated molecules with various interesting functional group by cross-metathesis were attempted for the two systems over Grubbs and Schrock catalyst. (1) Cross-metathesis of various kinds of vinylarene and vinylhetroaromatics with 1 -octene, and (2) Cross-metathesis reactions between vinylferrocene and a series of vinylarene. Self -metathesis of vinylferrocene was not occurred, but Interestingly cross-metathesis proceeded to yield heterodimer (cross-metathesis product) with high selectivity (73-100 %) in the presence of the Schrock catalyst. The mechanism of selective heterodimer formation was proposed.