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Issue 36, 2015
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The luminescence properties of heteroleptic [OsCl(CO)(N∩N)(P∩P)]+ complexes – radiative and non-radiative deactivation of the excited 3*MLCT state

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Abstract

The luminescence properties of the heteroleptic [OsCl(CO)(N∩N)(P∩P)]+ complexes with bidentate phosphine P∩P and diimine N∩N ligands have been studied in acetonitrile solutions at room temperature and in methanol/ethanol (1 : 1) glasses at 77 K. At room temperature the investigated complexes feature strong (with the quantum yields ϕem from 0.17 up to 0.64), long-lived (with lifetimes τem in the range of 1.5–44.2 μs) 3*MLCT emission. Analysis of 3*MLCT emission band shapes leads to the quantities relevant for the radiative electron transfer (between the Os2+ central ion and the N∩N ligand) in the Marcus inverted region. It is also demonstrated that radiative kr and non-radiative knr decay rate constants of the excited 3*MLCT states can be interpreted within the Mulliken–Hush formalism. Especially values of knr rate constants can be predicted using the parameters available from the analysis of the radiative 1*MLCT ← S0 and 3*MLCT → S0 charge transfer processes.

Graphical abstract: The luminescence properties of heteroleptic [OsCl(CO)(N∩N)(P∩P)]+ complexes – radiative and non-radiative deactivation of the excited 3*MLCT state

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Publication details

The article was received on 07 Jun 2015, accepted on 05 Aug 2015 and first published on 19 Aug 2015


Article type: Paper
DOI: 10.1039/C5CP03299G
Citation: Phys. Chem. Chem. Phys., 2015,17, 23332-23345
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    The luminescence properties of heteroleptic [OsCl(CO)(N∩N)(P∩P)]+ complexes – radiative and non-radiative deactivation of the excited 3*MLCT state

    A. Kamecka and A. Kapturkiewicz, Phys. Chem. Chem. Phys., 2015, 17, 23332
    DOI: 10.1039/C5CP03299G

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