Photochemical Oxidation of Pt(IV)Me<sub>3</sub>(1,2-diimine) Thiolates to Luminescent Pt(IV) Sulfinates

نویسندگان

چکیده

We report the formation of dinuclear complexes from, and photochemical oxidation of, (CH3)3-Pt(IV)(N^N) (N^N = 1,2-diimine derivatives) thiophenolate ligands to analogous sulfinates (CH3)3Pt(N^N)(SO2Ph) structural, spectroscopic, theoretical studies latter revealing tunable photophysics depending upon ligands. Electron-rich thiolate conjugated 1,2-diimines encourage thiolate-bridged complexes; smaller or electron-poor thiolates favor mononuclear complexes. Photooxidation ligand yields hitherto unreported Pt(IV)-SO2R complexes, promoted by electron-deficient such as 4-nitrothiophenol, which exclusively forms sulfinate complex. Such exhibit expected absorptions due π-π* transitions mixed with spin-allowed singlet MLCT (d-π*) at relatively high energy (270-290 nm), well unexpected broad, lower between 360 490 nm. DFT data indicate that these low absorption bands result from excitation Pt-S Pt-C σ-bonding electrons π* orbitals on 1,2-diimine, gives rise emission in visible range.

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ژورنال

عنوان ژورنال: Inorganic Chemistry

سال: 2021

ISSN: ['0020-1669', '1520-510X']

DOI: https://doi.org/10.1021/acs.inorgchem.0c03553