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

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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.