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  • Title: Oxidative quenching within photosensitizer-acceptor dyads based on bis(bidentate) phosphine-connected osmium(II) bipyridyl light absorbers and reactive metal sites.
    Author: Eller S, Trettenbrein B, Oberhuber D, Strabler C, Gutmann R, van der Veer WE, Ruetz M, Kopacka H, Obendorf D, Brüggeller P.
    Journal: Inorg Chem Commun; 2012 Sep; 23(6):41-45. PubMed ID: 23471298.
    Abstract:
    For the first time oxidative quenching of OsP2N4 chromophores by reactive PtII or PdII sites containing cis, trans, cis-1,2,3,4-tetrakis(diphenylphosphino)cyclobutane (dppcb) is directly observed despite the presence of a saturated cyclobutane backbone "bridge". This dramatic effect is measured as a sudden temperature-dependent onset of a reduction in phosphorescence lifetime in [Os(bpy)2(dppcb)MCl2](SbF6)2 (M = Pt, 1; Pd, 2). The appearance of this additional energy release is not detectable in [Os(bpy)2(dppcbO2)](PF6)2 (3), where dppcbO2 is cis, trans, cis-1,2-bis(diphenylphosphinoyl)-3,4-bis(diphenylphosphino)cyclobutane. Obviously, the square-planar metal centers in 1 and 2 are responsible for this effect. In line with these observations, the emission quantum yields at room temperature for 1 and 2 are drastically reduced compared with 3. Since this luminescence quenching implies strong intramolecular interaction between the OsII excited states and the acceptor sites and depends on the metal⋯metal distances, also the single crystal X-ray structures of 1-3 are given.
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