Construction and Function of One-dimensional Organometallic Composites Consisting of π-Conjugated Molecule and Metal Chain

π共轭分子与金属链组成的一维有机金属复合材料的构建与功能

基本信息

批准号：
13450370
负责人：
KUROSAWA Hideo
金额：
$ 7.49万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2002
项目状态：
已结题

项目摘要

Great attention has been paid to π-conjugated molecules such as polyacetylenes and polyphenylenes as functional organic materials, while one-dimensional polymetal wires also attract attention as inorganic functional materials and catalysts. The objective of the current project is to construct linear organometallic composites by combining these organic and inorganic conjugate systems via coordination bond, and to examine their catalytic and electric properties for application to the functional composites.We first attained the synthesis of Pd-Pd bonded complex containing six acetonitrile ligands, which suit for substitution by rather weakly coordinating unsaturated hydrocarbon ligands. This Pd-Pd complex reacted with 1,6-diphenylhexatriene to give sandwich complex in which two hexatriene ligands coordinate with the Pd-Pd moiety. The structure of the new sandwich complex was determined by X-ray crystallography. The reaction of a given polyene (double bond number = n) with acetonitrile Pd-Pd complex in the presence of n-3 equivalent Pd(0) afforded linear sandwich complex composed of (Pd)n-1 chain and two polyene ligands.We also found that photo-irradiation (>510 nm) at room temperature of Pd3-tetraene sandwich complex induces interconversion between meso and racemi isomers of this sandwich complex, while no such interconversion takes place under dark at room temperature. Treatment of the Pd3 sandwich with reducing or oxidizing reagent led to no similar isomerization.

聚乙炔和聚亚苯基等π共轭分子作为功能有机材料受到了极大的关注，而一维多金属线作为无机功能材料和催化剂也引起了人们的关注，当前项目的目标是通过结合来构建线性有机金属复合材料。通过配位键对这些有机和无机共轭体系进行了研究，并检查了它们在功能复合材料中的催化和电学性能。我们首先实现了Pd-Pd键合的合成含有六个乙腈配体的络合物，适合被弱配位的不饱和烃配体取代。该Pd-Pd络合物与1,6-二苯基己三烯反应，得到两个己三烯配体与Pd-Pd部分配位的夹心络合物。新的夹层络合物通过 X 射线晶体学测定给定的多烯（双键数 = n）与乙腈的反应。 Pd-Pd配合物在n-3当量的Pd(0)存在下提供了由(Pd)n-1链和两个多烯配体组成的线性夹心配合物。我们还发现室温下的光照射(>510 nm) Pd3-四烯夹心复合物诱导该夹心复合物的内消旋异构体和外消旋异构体之间的相互转化，而在室温下黑暗下不发生这种相互转化。用还原或氧化处理Pd3夹心。试剂没有导致类似的异构化。