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Photocatalytic function of the B-12 complex with the cyclometalated iridium(III) complex as a photosensitizer under visible light irradiation

Title
Photocatalytic function of the B-12 complex with the cyclometalated iridium(III) complex as a photosensitizer under visible light irradiation
Authors
Tian, HuiShimakoshi, HisashiPark, GyurimKim, SinheuiYou, YoungminHisaeda, Yoshio
Ewha Authors
유영민
SCOPUS Author ID
유영민scopus
Issue Date
2018
Journal Title
DALTON TRANSACTIONS
ISSN
1477-9226JCR Link1477-9234JCR Link
Citation
vol. 47, no. 3, pp. 675 - 683
Publisher
ROYAL SOC CHEMISTRY
Indexed
SCI; SCIE; SCOPUS WOS
Abstract
A visible light induced three-component catalytic system with the cobalamin derivative (B-12) 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 N-2 was developed. This catalytic system showed a much higher catalytic efficiency than the previous catalytic system using [Ru(II)(bpy)(3)]Cl-2 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 B-12, 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 B-12 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.
DOI
10.1039/c7dt03742b
Appears in Collections:
엘텍공과대학 > 화학신소재공학전공 > Journal papers
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