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A triangular prismatic hexanuclear iridium(iii) complex bridged by flavin analogues showing reversible redox processes

Title
A triangular prismatic hexanuclear iridium(iii) complex bridged by flavin analogues showing reversible redox processes
Authors
Inui Y.Shiro M.Kusukawa T.Fukuzumi S.Kojima T.
Ewha Authors
Shunichi Fukuzumi
SCOPUS Author ID
Shunichi Fukuzumiscopus
Issue Date
2013
Journal Title
Dalton Transactions
ISSN
1477-9226JCR Link
Citation
vol. 42, no. 8, pp. 2773 - 2778
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
[Ir6(μ-alloCl2 2-)3(Cp* )6(OH)3](PF6)3 (1) having 7,8-dichloroalloxazine dianion (alloCl2 2-) as bridging ligands was synthesized and characterized by X-ray crystallography, spectroscopic and electrochemical measurements. The alloxazine ligands showed unprecedented coordination modes to link the six Ir(iii) centres. The complex exhibited remarkable stability and reversible six-electron redox processes at the bridging alloxazine ligands in organic solvents. The first reversible reduction process occurred on each of three alloxazine ligands in 1 to produce a three-electron-reduced species, [IrIII 6Cp* 6(μ-alloCl2 3-)3(OH)3], and was observed as an apparent one-step reduction process at -0.65 V (vs. Fc0/+). The second reversible reduction process on each of the three alloxazine ligands in 1 was recorded at almost the same potential, -0.78 V (vs. Fc0/+), to afford the six-electron-reduced form, [Ir III 6Cp*6(μ-alloCl2 4-)3(OH)3]3-. The radical anion of the alloxazine derivative was detected by EPR measurements at room temperature. After the six-electron reduction of 1 with cobaltocene, the backward oxidation processes of reduced forms with p-chloranil were traced by UV-Vis spectroscopy to confirm the recovery of the original spectrum of 1. © 2013 The Royal Society of Chemistry.
DOI
10.1039/c2dt32535g
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자연과학대학 > 화학·나노과학전공 > Journal papers
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