Electronic state of metal complexes and dynamics of their electron transfer reactions

金属配合物的电子态及其电子转移反应的动力学

• 批准号: 03303005
• 负责人: OGINO Hiroshi
• 金额: $ 4.48万
• 依托单位: TOHOKU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Co-operative Research (A)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03303005/
• 关键词: metal complex; cluster; electron transfer; redox potential; mixed valence; photo-induced electron transfer; scanning tunneling microscope; 走査トンネル顕微鏡; 触媒; 機能性材料; 錯体; 電子状態; ダイナミックス; 光合成; トンネル顕微鏡; エネルギ-ギャップ則; 光誘起電荷分離; metal complex; cluster; electron transfer; redox potential; mixed valence; photo-induced electron transfer; scanning tunneling microscope; 走査トンネル顕微鏡; 触媒; 機能性材料; 錯体; 電子状態; ダイナミックス; 光合成; トンネル顕微鏡; エネルギ-ギャップ則; 光誘起電荷分離

A great progress was achieved for the synthesis of monomeric,dimeric,and polymeric metal complexes as well as metal clusters. Especially for several series of dimeric complexes, rational syntheses have became possible.On the basis of these synthetic results,the relation between electronic state of complexes and their redox potentials was investigated. Various novel electron transfer systems were discovered:System which generates mixed valence states accompanying with redox processes,electron transfer kinetics which obeys zero-th order rate law,electron transfer system which couples with proton transfer,and system which catalyzes the reduction of CO_2. Photo-induced electron transfer reactions of metal complexes were extensively investigated from both theoretical and experimental points of view. Structural analysis of chemical species produced on electrode surface was carried out with the aid of scanning tunneling microscope and provided useful information for the electron transfer at electrode-solution interface.These investigations were carried out by cooperative researches. Two symposia were held on November 11 and 12,1991(Tokyo)and November 11 and 12,1992(Okazaki) for discussing the results and exchanging ideas.We believe that our cooperative research was undertaken quite timely,since 1992 Nobel prize was awarded to Professor R.A.Marcus who made a great contribution on electron transfer theory in chemical system.

对于单体，二聚体和聚合物金属配合物以及金属簇的合成，取得了巨大的进步。特别是对于几个系列二聚体复合物，有理合成已成为可能。在这些合成结果的基础上，研究了复合物的电子状态及其氧化还原电位之间的关系。发现了各种新型电子传输系统：伴随氧化还原过程，电子传递动力学的系统，遵守零订单速率定律，电子传输系统，这些系统将其与质子传递相结合，以及催化CO_2降低的系统。从理论和实验观点都广泛研究了金属复合物的光诱导的电子传递反应。借助扫描隧道显微镜进行了在电极表面产生的化学物种的结构分析，并为电极溶液接口时的电子传输提供了有用的信息。这些研究是由合作研究进行的。 1991年11月11日至12日（东京）和1992年11月11日至1992年12月12日（冈萨基）举行了两次座谈会，以讨论结果并交换想法。我们相信，自1992年以来，我们的合作研究是非常及时进行的，自1992年以来，诺贝尔奖就授予了R.A.Marcus教授对Marcus的贡献，他对Electron System进行了很好的贡献。