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A combined experimental and theoretical study on a single, unsupported oxo-bridged Mn(iii,iii) dimer coordinated to two iminobenzosemiquinone π-radical anions

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    SYSNO ASEP0543394
    Document TypeJ - Journal Article
    R&D Document TypeJournal Article
    Subsidiary JČlánek ve WOS
    TitleA combined experimental and theoretical study on a single, unsupported oxo-bridged Mn(iii,iii) dimer coordinated to two iminobenzosemiquinone π-radical anions
    Author(s) Paul, G. C. (IN)
    Sarkar, P. (IN)
    Sarmah, Amrit (UOCHB-X) ORCID
    Shaw, P. (IN)
    Maity, S. (IN)
    Mukherjee, C. (IN)
    Source TitleDalton Transactions. - : Royal Society of Chemistry - ISSN 1477-9226
    Roč. 50, č. 25 (2021), s. 8768-8775
    Number of pages8 s.
    Languageeng - English
    CountryGB - United Kingdom
    Keywordstransition-metal-complexes ; manganese(iii) complexes ; dimanganese complexes
    OECD categoryPhysical chemistry
    R&D ProjectsGBP208/12/G016 GA ČR - Czech Science Foundation (CSF)
    GX19-27454X GA ČR - Czech Science Foundation (CSF)
    Method of publishingLimited access
    Institutional supportUOCHB-X - RVO:61388963
    UT WOS000657790000001
    EID SCOPUS85108868156
    DOI10.1039/d1dt00489a
    AnnotationLigand H2LAP comprises a non-innocent 2-aminophenol unit and an innocent bis(pyridin-2-ylmethyl)amine unit. The ligand, upon reaction with an equivalent amount of Mn(ClO4)2·6H2O in the presence of Et3N under air in MeOH, provided a mono(oxo)-bridged dinuclear Mn2 complex ({[(LISQ)MnIII–O–MnIII(LISQ)][(ClO4)]2}, 1). X-ray crystal structure analysis of complex 1 revealed that in the dicationic unit, the physical oxidation state of each Mn ion was +III and the 2-aminophenol unit of ligand H2LAP was in its one-electron oxidized iminobenzosemiquinone form. 1H-NMR measurement of complex 1 confirmed that the complex acquired a diamagnetic ground state (St = 0). Thus, antiferromagnetic couplings among the paramagnetic centers were realized. The UV-Vis-NIR spectrum of complex 1 was consisted of ligand-to-metal charge-transfer transitions in the visible region, while ligand-to-metal and metal-to-ligand charge-transfer transitions were noticed in the near-infrared region due to the presence of iminobenzosemiquinone radical units. The cyclic voltammogram of the complex showed three one-electron oxidation waves and two one-electron reduction waves. While the first two oxidation processes were metal-based, the two successive reductions were ligand-centered. DFT-based theoretical studies confirmed the assignment.
    WorkplaceInstitute of Organic Chemistry and Biochemistry
    Contactasep@uochb.cas.cz ; Kateřina Šperková, Tel.: 232 002 584 ; Jana Procházková, Tel.: 220 183 418
    Year of Publishing2022
    Electronic addresshttps://doi.org/10.1039/D1DT00489A
Number of the records: 1  

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