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

σ-π杂化共轭分子有望成为具有高透明性和光学非线性的新型有机材料。本文首次尝试了烯烃复分解法合成聚（硅烯-乙烯烯）。以Re_2O_7-Al_2O_3为催化剂，四乙烯基硅烷、二甲基二乙烯基硅烷和1，4-双（二甲基乙烯基硅基）苯在温和的反应条件下进行自复分解，合成了线型低聚（硅烯-乙烯烯）（二聚体-乙烯烯）。发现它们是具有高透明性的σ-π杂化共轭分子，但不能得到更高的低聚物和聚合物。光谱研究表明，它们的光学非线性很弱，二茂铁是一种有趣的具有光学非线性的化合物，我们尝试了在Grubbs和Schrock催化剂上通过交叉复分解反应选择性地合成具有各种有趣官能团的π共轭分子. (1)各种乙烯基芳烃和乙烯基杂芳烃与1 -辛烯的交叉复分解反应;（2）乙烯基二茂铁与一系列乙烯基芳烃的交叉复分解反应。没有发生乙烯基二茂铁的自复分解，但有趣的是，在Schrock催化剂的存在下，交叉复分解进行以高选择性（73- 100%）产生异二聚体（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.