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  • Photochemical Oxidation of Pt(IV)Me3(1,2-Diimine) Thiolates to Luminescent Pt(IV)Sulphinates

    Rights statement: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c03553

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Photochemical Oxidation of Pt(IV)Me3(1,2-diimine) Thiolates to Luminescent Pt(IV) Sulfinates

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Photochemical Oxidation of Pt(IV)Me3(1,2-diimine) Thiolates to Luminescent Pt(IV) Sulfinates. / Mala, Bara; Murtagh, Laura; Farrow, Charlotte; Akien, Geoffrey; Halcovitch, Nathan; Allinson, Sarah; Platts, James A.; Coogan, Michael.

In: Inorganic Chemistry, Vol. 60, No. 10, 17.05.2021, p. 7031-7043.

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Mala, Bara ; Murtagh, Laura ; Farrow, Charlotte ; Akien, Geoffrey ; Halcovitch, Nathan ; Allinson, Sarah ; Platts, James A. ; Coogan, Michael. / Photochemical Oxidation of Pt(IV)Me3(1,2-diimine) Thiolates to Luminescent Pt(IV) Sulfinates. In: Inorganic Chemistry. 2021 ; Vol. 60, No. 10. pp. 7031-7043.

Bibtex

@article{8d57d03b1b7a4250afd4cc9ad52eb531,
title = "Photochemical Oxidation of Pt(IV)Me3(1,2-diimine) Thiolates to Luminescent Pt(IV) Sulfinates",
abstract = "We report the formation of dinuclear complexes from, and photochemical oxidation of, (CH3)3-Pt(IV)(N^N) (N^N = 1,2-diimine derivatives) complexes of thiophenolate ligands to the analogous sulfinates (CH3)3Pt(N^N)(SO2Ph) and structural, spectroscopic, and theoretical studies of the latter revealing tunable photophysics depending upon the 1,2-diimine ligands. Electron-rich thiolate and conjugated 1,2-diimines encourage formation of thiolate-bridged dinuclear complexes; smaller 1,2-diimines or electron-poor thiolates favor mononuclear complexes. Photooxidation of the thiolate ligand yields hitherto unreported Pt(IV)-SO2R complexes, promoted by electron-deficient thiolates such as 4-nitrothiophenol, which exclusively forms the sulfinate complex. Such complexes exhibit expected absorptions due to π-π* ligand transitions of the 1,2-diimines mixed with spin-allowed singlet MLCT (d-π*) at relatively high energy (270–290 nm), as well as unexpected broad, lower energy absorptions between 360 and 490 nm. DFT data indicate that these low energy absorption bands result from excitation of Pt–S and Pt–C σ-bonding electrons to π* orbitals on sulfinate and 1,2-diimine, the latter of which gives rise to emission in the visible range.",
author = "Bara Mala and Laura Murtagh and Charlotte Farrow and Geoffrey Akien and Nathan Halcovitch and Sarah Allinson and Platts, {James A.} and Michael Coogan",
note = "This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright {\textcopyright} American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c03553",
year = "2021",
month = may,
day = "17",
doi = "10.1021/acs.inorgchem.0c03553",
language = "English",
volume = "60",
pages = "7031--7043",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "10",

}

RIS

TY - JOUR

T1 - Photochemical Oxidation of Pt(IV)Me3(1,2-diimine) Thiolates to Luminescent Pt(IV) Sulfinates

AU - Mala, Bara

AU - Murtagh, Laura

AU - Farrow, Charlotte

AU - Akien, Geoffrey

AU - Halcovitch, Nathan

AU - Allinson, Sarah

AU - Platts, James A.

AU - Coogan, Michael

N1 - This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c03553

PY - 2021/5/17

Y1 - 2021/5/17

N2 - We report the formation of dinuclear complexes from, and photochemical oxidation of, (CH3)3-Pt(IV)(N^N) (N^N = 1,2-diimine derivatives) complexes of thiophenolate ligands to the analogous sulfinates (CH3)3Pt(N^N)(SO2Ph) and structural, spectroscopic, and theoretical studies of the latter revealing tunable photophysics depending upon the 1,2-diimine ligands. Electron-rich thiolate and conjugated 1,2-diimines encourage formation of thiolate-bridged dinuclear complexes; smaller 1,2-diimines or electron-poor thiolates favor mononuclear complexes. Photooxidation of the thiolate ligand yields hitherto unreported Pt(IV)-SO2R complexes, promoted by electron-deficient thiolates such as 4-nitrothiophenol, which exclusively forms the sulfinate complex. Such complexes exhibit expected absorptions due to π-π* ligand transitions of the 1,2-diimines mixed with spin-allowed singlet MLCT (d-π*) at relatively high energy (270–290 nm), as well as unexpected broad, lower energy absorptions between 360 and 490 nm. DFT data indicate that these low energy absorption bands result from excitation of Pt–S and Pt–C σ-bonding electrons to π* orbitals on sulfinate and 1,2-diimine, the latter of which gives rise to emission in the visible range.

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

U2 - 10.1021/acs.inorgchem.0c03553

DO - 10.1021/acs.inorgchem.0c03553

M3 - Journal article

VL - 60

SP - 7031

EP - 7043

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 10

ER -