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A theoretical study on charge transfer and other properties induced by conformation conversion of ligands in Ru complexes

钌配合物中配体构象转变引起的电荷转移及其他性质的理论研究

基本信息

批准号：
16550001
负责人：
NORO Takeshi
金额：
$ 1.86万
依托单位：
Hokkaido University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2005
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16550001/
关键词：
Ru complex Charge transfer and ligands conformation conversion of ligands photo-induced long lived metastable state potential surface redox process exicited state [Ru(CN)_5NO]^<2->光誘起長寿命準安定状態スイッチング素子無輻射遷移 Ru_3O(CH_3CO_2)_6L_2CO

项目摘要

The second row transition metal complexes show higher covalency than the first row transition metal complexes, and exhibit chemically interesting properties. In this study, we take complexes including Ru which is equivalent to Fe and investigate electronic structures of primarily [Ru(III)L_5NO]^<2->, and Ru_3O(CH_3CO_2)_6L_2CO. These materials have been paid special attention in the field of transition metal complexes and tried to develop them in the biological or electronics as well as subject of fundamental studies. These types of complexes show unique properties induced by charge transfer and conformation conversion of ligands.[Ru(III)L_5NO] (L=CN^-) ; The crystal of this complex has two extremely long-lived photo-induced meta stable states. This is expected to be a promising switching material. In this study, we took [Fe(III)L_5NO] as well as [Ru(III)L_5NO] and studied the structure of the ground state and two meta stable states, and barrier heights among them, using ab initio calc … More ulations. Further more global excited state potential surfaces were calculated and explained possible photo induced isomerization among the meta stable and ground states by non-adiabatic transition. The high covalency in Ru complex cause higher potential barrier than in Fe complex and it is the origin of the longer life-time in Ru complex than in Fe complex.Ru_3O (CH_3CO_2)_6L_2CO (L=bzpy) ; We reported the electronic structure of [Ru_3O(CH_3CO_2)_6(bzpy)_2CO]^n (n=-2〜0, bzpy=4-benzoylpyridine) and relative stability of the isomers, using results of ab initio molecular orbital calculations. Recently, Tanaka et al. reported that the complex, Ru_3O(CH_3CO_2)_6L_2CO, shows six one-electron reversible redox processes. In their work, two slightly different C-O vibrational frequencies were obtained only for the 2 electron reduction species of this complex in CH_2Cl_2 solution, whereas only one C-O vibrational mode in the other species. This suggests that there exists two types of isomers in doubly reduced one. In the present calculation, we found the global minimum at the dihedral angle between the Ru_3-O plane and bzpy plane was almost 90° (perpendicular). The planer structure (0, 180°) was the local minimum. For the 2 electron reduction species, there were two minima at a planer structure and a perpendicular structure whose total energies are close to one another. This seems to explain the two C-O different vibrational modes. Less

第二行过渡金属配合物比第一行过渡金属配合物具有更高的共价，并表现出有趣的化学性质。在本研究中，我们选取了含有相当于Fe的Ru配合物，主要研究了[Ru(III)L_5NO]^<2->和Ru_3O(CH_3CO_2)_6L_2CO的电子结构。这些材料在过渡金属配合物领域受到了特别的关注，并试图在生物或电子以及基础研究的主题中发展它们。这些类型的配合物表现出由配体的电荷转移和构象转换引起的独特性质。[Ru(III)L_5NO] (L=CN^-)；这种配合物的晶体具有两种极长寿命的光致元稳定状态。这有望成为一种有前途的开关材料。本研究以[Fe(III)L_5NO]和[Ru(III)L_5NO]为例，采用从头算方法研究了基态和两个元稳定态的结构，以及它们之间的势垒高度。进一步计算了全局激发态势面，并解释了在元稳定态和基态之间通过非绝热跃迁可能发生的光致异构化。钌配合物的高共价导致其电位势垒高于铁配合物，这是钌配合物寿命比铁配合物长的原因。Ru_3O (CH_3CO_2)_6L_2CO (L=bzpy)；利用从头算分子轨道计算结果，报道了[Ru_3O(CH_3CO_2)_6(bzpy)_2CO]^n （n=-2 ~ 0, bzpy=4-苯甲酰吡啶）的电子结构和相对稳定性。最近，Tanaka等人报道了络合物Ru_3O(CH_3CO_2)_6L_2CO表现出6个单电子可逆氧化还原过程。在他们的工作中，该配合物在CH_2Cl_2溶液中，只有2个电子还原组分获得了两个略有不同的C-O振动频率，而在其他组分中只有一个C-O振动模式。这表明双重还原的异构体中存在两种类型的异构体。在本计算中，我们发现Ru_3-O平面与bzpy平面之间的二面角的全局最小值几乎为90°（垂直）。刨床结构（0,180°）是局部最小值。对于2种电子还原物质，在平面结构和垂直结构处存在两个极小值，两者的总能量相近。这似乎解释了两种C-O不同的振动模式。少