MLCT interaction in [Rh(II)2(CO3)4]4 −( x L) |
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| Affiliation: | 1. Center of New Technologies, University of Warsaw, Żwirki i Wigury 93, 02089, Warsaw Poland;2. Faculty of Chemistry, University of Warsaw, Pasteur 1, 02093, Warsaw, Poland;3. The Czochralski Laboratory of Advanced Crystal Engineering, Faculty of Chemistry, University of Warsaw, Żwirki i Wigury 101, 02089, Warsaw, Poland;4. Department of Inorganic Chemistry and Technology, Jožef Stefan Institute, Jamova cesta 39, 1000, Ljubljana, Slovenia;1. Key Laboratory of Polymer and Catalyst Synthesis Technology of Liaoning Province, School of Environmental and Chemical Engineering, Shenyang University of Technology, Shenyang 110870, China;2. CAS Key Laboratory of Nuclear Materials and Safety Assessment, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China;1. Department of Pure and Applied Chemistry, Faculty of Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510, Japan;2. Division of Ecosystem Research, Research Institute for Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510, Japan |
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| Abstract: | Complexes of the type RhII2(CO3)4(H2O)L]n − with L = N-methylpyrazinium+ and 1-heptyl-4-(4-pyridinyl)pyridinium+ cations display intense long-wavelength (Rh(II) to L) MLCT absorptions. With L = H2O, MLCT absorptions are not identified, but the photoreactivity of the complex in aqueous solution supports the assumption that (Rh(II) to CO32 −) MLCT excited states are accessible. Upon irradiation with white light, Rh(II) is photooxidized while carbonate is reduced to CO. The efficiency of this photolysis is very low. However, the occurrence of this photoredox reaction is, nevertheless, of general interest with regard to the photochemical reduction of CO2. |
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