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Synthesis and photo-catalytic carbon dioxide reduction property of dinuclear rhenium (I) complexes

双核铼(I)配合物的合成及其光催化二氧化碳还原性能

基本信息

批准号：
17550051
负责人：
KITA Shouichi
金额：
$ 2.46万
依托单位：
Hirosaki University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2005
资助国家：
日本
起止时间：
2005 至 2007
项目状态：
已结题

项目摘要

It is known that rhenium (I) tricarbonyl di-imine complexes works as the photocatalyst which selectively reduces the carbon dioxide to carbon monoxide under the existence of weak reducing agent. The polynuclear metal complexes have attracted interest as two electrons reduction catalyst of such reaction.1. Two novel ligand, bdpbiaH_2=1,8-bis(dipyrido-[2,3-e:2',3'-g]-1H-benzoimidazole)anthracene and bdpbibH_2=1,8-bis(dipyrido-[2,3-e:2'',3''-g]-1H-benzoimidazole)benzene which could closely combine two metal core to each other, was designed, and rhenium (I) or ruthenium (II) binuclear complex were synthesized using these bridging ligand. These complexes may be able to activate the small molecule like carbon dioxide in two metal core. The ligands and complexes were identified by elemental analysis and MALDI-TOF mass spectrometric analysis.2. Both ligands showed the intense fluorescence in fluid solution at ambient temperature. BdpbibH2 ligand showed the broad emission which seemed to be the intramolecular excimer emission at room temperature in the long wavelength region. The UV-visible absorption and the emission spectra, and the electrochemistry measurement of binuclear metal complexes show that the only weak interactions work between two metal centers.3. The geometry optimization calculations by the density functional theory (DFT) show that the distances between two metal.cores (7~11A) are sufficient in order to insert molecules such as the carbon dioxide. But the synergic effect of the photo catalytic reduction abilities of carbon dioxide could not be observed.The part of the result was reported in 20th Conference on Photochemistry and Photophysics of Coordination Compound, and 57th Annual Meetings of Japan Society of Coordination Chemistry.

已知双（I）三羰基二亚胺配合物作为光催化剂在弱还原剂存在下选择性地将二氧化碳还原为一氧化碳。多核金属配合物作为双电子还原反应的催化剂引起了人们的兴趣.设计了两个新的配体bdpbiaH_2= 1，8-双（联吡啶并[2，3-e：2 '，3'-g]-1H-苯并咪唑）蒽和bdpbibH_2= 1，8-双（联吡啶并[2，3-e：2 ''，3 ''-g]-1H-苯并咪唑）苯，它们能将两个金属核紧密地联合收割机结合在一起，并以此为桥联配体合成了钌（I）或钌（II）双核配合物。这些配合物可能能够激活像二氧化碳这样的小分子中的两个金属核。通过元素分析和MALDI-TOF质谱分析对配体和配合物进行了结构鉴定.两种配体在室温下的流体溶液中都显示出强烈的荧光。BdpbibH_2配体在室温下在长波长范围内具有较宽的发射峰，类似于分子内激基缔合物的发射。双核金属配合物的紫外-可见吸收光谱、发射光谱和电化学测试表明，双核金属配合物中只有两个金属中心之间存在微弱的相互作用.用密度泛函理论（DFT）进行的几何优化计算表明，两个金属核之间的距离（7~ 11 A）足以插入二氧化碳等分子。这部分结果已在第20届配位化合物光化学和光物理会议和第57届日本配位化学学会年会上发表。