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• W2321685715 endingPage "11805" @default.
• W2321685715 startingPage "11798" @default.
• W2321685715 abstract "A series of dinuclear cobalt complexes of general formula [Co(Mentpa)(diox-S-diox)Co(Mentpa)](PF6)2·MeOH (n = 0, 2, 3) was prepared through the synthesis of the bis-bidentate ligand 6,6'-((1,4-phenylenebis(methylene))bis(sulfanediyl))bis(3,5-di-tert-butyl-benzene-1,2-diol) (diox-S-diox). The ancillary ligands Mentpa are obtained by the tripodal tris(2-pyridylmethyl)amine (tpa) ligand through successive introduction of methyl groups into the 6 position of the pyridine moieties. As expected, the steric hindrance induced by this substitution modulates the redox properties of the metal acceptor, determining the charge distribution of the metal-dioxolene adduct at room temperature. Magnetic measurements and X-ray photoelectron and X-ray absorption spectroscopies indicate that the charge distributions low-spin-Co(III)-catecholate and high-spin-Co(II)-semiquinonate characterize the complexes formed by the tpa and Me3tpa tetradentate ligands, respectively. The complex formed by the Me2tpa ligand undergoes a thermal- and light-induced interconversion of the two states, in agreement with the existence of a valence tautomeric equilibrium. All complexes were stable and behaved reproducibly under X-ray irradiation. This work points out a fast and simple chemical approach to structurally and electronically modify the catechol ring while leaving its coordination capabilities unaffected. These findings afford a robust chemical method to prepare sulfur-functionalized dioxolene ligands as new molecular bricks for chemical functionalization of noble metal surfaces with this class of molecular switches." @default.
• W2321685715 created "2016-06-24" @default.
• W2321685715 creator A5010445451 @default.
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• W2321685715 creator A5083074516 @default.
• W2321685715 date "2013-10-04" @default.
• W2321685715 modified "2023-09-30" @default.
• W2321685715 title "Magnetic and Spectroscopic Investigation of Thermally and Optically Driven Valence Tautomerism in Thioether-Bridged Dinuclear Cobalt–Dioxolene Complexes" @default.
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• W2321685715 doi "https://doi.org/10.1021/ic4011949" @default.
• W2321685715 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/24090074" @default.
• W2321685715 hasPublicationYear "2013" @default.
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