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Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts
Published on: August 7, 2018
Supramolecular multi-electron redox photosensitisers comprising a ring-shaped Re(i) tetranuclear complex and a
Maria Takahashi1, Tsuyoshi Asatani1, Tatsuki Morimoto2
1Department of Chemistry, School of Science, Tokyo Institute of Technology O-okayama 2-12-1-NE-1 Meguro-ku Tokyo 152-8550 Japan ishitani@chem.titech.ac.jp.
Abstract:
Redox photosensitisers (PSs) play essential roles in various photocatalytic reactions. Herein, we synthesised new redox PSs of 1 : 1 supramolecules that comprise a ring-shaped Re(i) tetranuclear complex with 4+ charges and a Keggin-type heteropolyoxometalate with 4- charges. These PSs photochemically accumulate multi-electrons in one molecule (three or four electrons) in the presence of an electron donor and can supply electrons with different reduction potentials. PSs were successfully applied in the photocatalytic reduction of CO2 using catalysts (Ru(ii) and Re(i) complexes) and triethanolamine as a reductant. In photocatalytic reactions, these supramolecular PSs supply a different number of electrons to the catalyst depending on the redox potential of the intermediate, which is made from the one-electron-reduced species of the catalyst and CO2. Based on these data, information on the reduction potentials of the intermediates was obtained.
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