Creation of multi-dimensional structures of functional molecules by metal complexation reactions

通过金属络合反应创建功能分子的多维结构

基本信息

批准号：
11309003
负责人：
NISHIHARA Hiroshi
金额：
$ 19.69万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2001
项目状态：
已结题

项目摘要

To construct new multi-dimensional functional molecular systems by utilizing complex reactions of transition metal complexes has been investigated in this research project. The molecular systems that have been focused are 1) azo-conjugated metal complexes with photo-functions, 2) donor-acceptor conjugated complexes with an ability of proton-coupled intramolecular electron-transfer reactions, and 3) metal nanoparticles modified with redox- and photo-functional complexes. The summary of the results is as follows.The trans-to-cis isomerization of azoferrocene proceeds not only by the photoexcitation of the π-π^* transition band but also by photoexcitation of the MLCT (d-π^* transition) band. The trans/cis ratio of the azobenzene-attached bipyridine ligands in their cobalt complex is reversibly altered by a combination of photoirradiation with a single UV light source and the reversible redox change between Co(II) and Co(III). A newly synthesized Ni, Pd and Pt tolylazophenylenedithiolato c … More omplexes 2-4 show reversible trans-to-cis photoisomerization, proto-chromism, and novel proton-coupled cis-to-trans isomerization.The protonation to carbonyl groups of the anthraquinone moiety in 1 -ferrocenylethynylanthraquinone causes intramolecular electron transfer leading to a novel structural change into a η^6-fulvene-cumulene Fe(II) complex. A 2:1 donor-acceptor complex, l,5-bis(ferrocenylethynyl)anthraquinone undergoes a two-step proton response, and the doubly protonated species involves a η^6-fulvene-Fe(II) complex-cumulene structure, and a novel spin-separated form of a ferrocenium (Fe(III)) ion and a semiquinone radical in the solution. Furthermore, the complex is in a thermal equilibrium between the valence tautomers of a donor-acceptor system in the solid state.Synthesis and electrochemical deposition behavior of biferrocene and anthraquinone derivative-modified Au and Pd clusters have been investigated. It is also possible to fabricate hetero structures by alternative electrodeposition of Bfc-modified gold and palladium nanoparticles. Less

本研究项目研究了利用过渡金属配合物的复杂反应构建新的多维功能分子系统，重点关注的分子系统是1）具有光功能的偶氮共轭金属配合物，2）供体-受体。具有质子耦合分子内电子转移反应能力的共轭络合物，以及3)用氧化还原和光功能络合物修饰的金属纳米颗粒。结果总结如下。偶氮二茂铁的反式异构化不仅通过 π-π^* 过渡带的光激发进行，还通过 MLCT（d-π^* 过渡）带的光激发进行。钴配合物中的联吡啶配体可通过单一紫外光源的光照射以及 Co(II) 和 Co(II) 之间的可逆氧化还原变化相结合而发生可逆改变。新合成的 Ni、Pd 和 Pt 甲苯基苯并二硫醇配合物 2-4 表现出可逆的反式到顺式光异构化、原色现象和新型质子耦合顺式到反式异构化。质子化为羰基1-二茂铁基乙炔基蒽醌中的蒽醌部分基团引起分子内电子转移，从而导致η^6-富烯-累积烯 Fe(II) 络合物的新颖结构变化 2:1 供体-受体络合物，l,5-双（二茂铁乙炔基）蒽醌经历两步质子反应，并且双质子化物质涉及。 η^6-fulvene-Fe(II) 复合积聚烯结构，以及二茂铁 (Fe(III)) 的新型自旋分离形式此外，该配合物在固态供体-受体系统的价态互变异构体之间处于热平衡状态。联二茂铁和蒽醌衍生物修饰的Au和Pd团簇的合成和电化学沉积行为。还可以通过 Bfc 修饰的金和钯纳米颗粒的交替电沉积来制造异质结构。