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Photocatalytic function of the B12 complex with the cyclometalated iridium(III) complex as a photosensitizer under visible light irradiation

Title
Photocatalytic function of the B12 complex with the cyclometalated iridium(III) complex as a photosensitizer under visible light irradiation
Authors
Tian H.Shimakoshi H.Park G.Kim S.You Y.Hisaeda Y.
Ewha Authors
유영민
SCOPUS Author ID
유영민scopus
Issue Date
2017
Journal Title
Dalton Transactions
ISSN
1477-9226JCR Link
Citation
Dalton Transactions vol. 47, no. 3, pp. 675 - 683
Publisher
Royal Society of Chemistry
Indexed
SCI; SCIE; SCOPUS WOS scopus
Document Type
Article
Abstract
A visible light induced three-component catalytic system with the cobalamin derivative (B12) as a catalyst, the cyclometalated iridium(iii) complex (Irdfppy, Irppy, Irpbt and [Ir{dF(CF3)ppy}2(dtbpy)]PF6) as a photosensitizer and triethanolamine as an electron source under N2 was developed. This catalytic system showed a much higher catalytic efficiency than the previous catalytic system using [Ru(ii)(bpy)3]Cl2 as the photosensitizer for the dechlorination reaction of 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT). Noteworthy is the fact that the remarkable high turnover number (over ten thousand) based on B12, which ranks at the top among the reported studies, was obtained when Irdfppy was used as a photosensitizer. This photocatalytic system was also successfully applied to the B12 enzyme-mimic reaction, i.e., the 1,2-migration of the phenyl group of 2-bromomethyl-2-phenylmalonate. The plausible reaction mechanism was proposed, which involved two quenching pathways, an oxidative quenching pathway and a reductive quenching pathway, to be responsible for the initial electron transfer of the excited-state photosensitizers during the DDT dechlorination reaction. Transient photoluminescence experiments revealed that the oxidative quenching of the photosensitizer dominated over the reductive quenching pathway. © The Royal Society of Chemistry 2017.
DOI
10.1039/c7dt03742b
Appears in Collections:
엘텍공과대학 > 화학신소재공학전공 > Journal papers
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