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アリールホウ素置換基を有する遷移金属錯体を利用した新規人工光合成系の創製

使用带有芳基硼取代基的过渡金属配合物创建新型人工光合作用系统

基本信息

批准号：
13J01659
负责人：
康媛媛
金额：
$ 1.73万
依托单位：
Hokkaido University
依托单位国家：
日本
项目类别：
Grant-in-Aid for JSPS Fellows
财政年份：
2013
资助国家：
日本
起止时间：
2013-04-01 至 2016-03-31
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13J01659/
关键词：
Re(I) complexes arylborane units X-ray crystallography CO2 reduction aritificial photosynthesis rhenium(I) tricarbonyl charge transfer photosynthesis system tricarbonyl rhenium complex charge transfer unit CO_2 reduction

项目摘要

Recently, energy shortage from fossil fuels and pollution of the environments have been two largest issues to be solved in the world. Therefore, solar energy has been focused as a sustainable energy source and its utilization has been one of the important research topics. Chemical approaches toward artificial photosynthesis utilizing transition metal complexes have been studied in the past decades. In particular, a tricarbonyl rhenium(I) complex having an aromatic diimine ligand, [Re(CO)3LX], has been received extensive attention due to the unique spectroscopic, photophysical, and photoredox properties.Until now, four novel tricarbonyl rhenium(I) complexes having one or two arylborane charge transfer unit(s) ReBphen/ReB2phen or ReBbpy/ ReB2bpy were　designed/synthesized and the spectroscopic/photophysical properties were studied in detail.Then, X-ray crystallographic analysis of ReB2phen was conduceted. The results agree very well with the predicted structure of it, where the rhenium(I) center adopts a nearly octahedral coordination geometry and the carbonyl ligands are arranged in a facial orientation.Furthermore, the photocatalytic activities of them towards CO2 reduction were studied by photoirradiation of the complexes in DMF/TEOA solutions under CO2 gas atmosphere. All of the complexes were shown to be the active catalysts for CO2 photoreduction, although its efficiency was dependent on the nature of the complex. However, the arylborane complexes showed lower turnover numbers (TON) for CO2 formation compared to the reference complexes without arylborane units.

近年来，化石燃料能源短缺和环境污染成为世界亟待解决的两大问题。因此，太阳能作为一种可持续能源受到关注，其利用已成为重要的研究课题之一。在过去的几十年里，人们已经研究了利用过渡金属配合物进行人工光合作用的化学方法。特别是具有芳香族二亚胺配体[Re(CO)3LX]的三羰基铼(I)配合物，由于其独特的光谱、光物理和光氧化还原性质而受到广泛关注。迄今为止，已有四种新型三羰基铼(I)配合物具有一个或两个芳基硼烷电荷转移单元ReBphen/ReB2phen或ReBbpy/ReB2bpy 设计/合成了ReB2phen，并对其光谱/光物理性质进行了详细研究。然后，对ReB2phen进行了X射线晶体学分析。结果与预测的结构非常吻合，其中铼(I)中心采用近八面体的配位几何形状，羰基配体呈面状排列。此外，通过在CO2气氛下对DMF/TEOA溶液中的配合物进行光照射，研究了它们对CO2还原的光催化活性。所有配合物均被证明是二氧化碳光还原的活性催化剂，尽管其效率取决于配合物的性质。然而，与不含芳基硼烷单元的参考复合物相比，芳基硼烷复合物显示出较低的 CO2 形成周转数 (TON)。

项目成果

期刊论文数量（0）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Photophysical and Photochemical Studies on Novel Tricarbonyl Rhenium(I) Complexes with Multiple-Arylboron Charge Transfer Units

具有多个芳基硼电荷转移单元的新型三羰基铼(I)配合物的光物理和光化学研究

DOI：
发表时间：
2014
期刊：
影响因子：
0
作者：
Yuanyuan Kang;Akitaka Ito;Eri Sakuda and Noboru Kitamura
通讯作者：
Eri Sakuda and Noboru Kitamura

アリールホウ素置換基を有するトリカルボニルレニウム(I)錯体の光化学物性に対するジイミン配位子の効果

二亚胺配体对芳基硼取代基三羰基铼(I)配合物光化学性质的影响

DOI：
发表时间：
2013
期刊：
影响因子：
0
作者：
Yusuke Yamashiro;Yasuhide Ohno;Kenzo Maehashi;Koichi Inoue;and Kazuhiko Matsumoto;康媛媛・伊藤亮孝・作田絵里・喜多村昇
通讯作者：
康媛媛・伊藤亮孝・作田絵里・喜多村昇

Diimine Ligand Variation Effects on Photophysical Properties of Novel Tricarbonyl Rhenium(I) Complexes Having Arylborane Charge Transfer Units

二亚胺配体变化对具有芳基硼烷电荷转移单元的新型三羰基铼(I)配合物光物理性质的影响