title: Facile Approaches to Phosphorescent Bis(cyclometalated) Pentafluorophenyl PtIVComplexes: Photophysics and Computational Studies.
abstract: A convenient and general strategy for the synthesis of stable bis(cyclometalated) pentafluorophenyl PtIVcomplexes fac-[Pt(C^N)2(C6F5)Cl] (3 a-f) and mer-[Pt(C^N)2(C6F5)(CN)] (4 c,d) has been developed. Complexes 3 were selectively generated by low-temperature oxidation of the cyclometalated PtIIcomplexes [Pt(C^N)(HC^N)(C6F5)] 2 [prepared from cis-[Pt(C6F5)2(HC^N)2] (1) intermediates] with PhICl2and subsequent metalation of the pendant HC^N ligand. Complexes 3 a,b were also alternatively generated by irradiation (Hg lamp, 400 W) of complexes 2 a,b, respectively, in CH2Cl2. This latter reaction proceeds via the hydride PtIVspecies cis-[Pt(C^N)2(C6F5)H], detected as the only intermediate species. The molecular structures of 1 a,d, 2 a, and 3 a,b,d,e were confirmed by X-ray diffraction. The substitution of Cl-by CN-in fac-[Pt(C^N)2(C6F5)Cl] [C^N=2-phenylbenzothiazole (3 c), 2-(4-bromophenyl)benzothiazole (3 d)] evolved with isomerization to give rise to the isomers (OC-6-42)-[Pt(C^N)2(C6F5)(CN)] (4 c, 4 d) having a mer disposition of the cyclometalated and C6F5groups (X-ray, 4 c). All the complexes are luminescent and their electronic spectra have been compared and interpreted with the aid of time-dependent DFT calculations.
authors.affiliation: Departamento de Química-Centro de Síntesis Química de La Rioja (CISQ), Universidad de La Rioja, 26006, Logroño, Spain.
authors.forename: Nora
authors.initials: N
authors.lastname: Giménez
authors.affiliation: Departamento de Química-Centro de Síntesis Química de La Rioja (CISQ), Universidad de La Rioja, 26006, Logroño, Spain.
authors.forename: Rebeca
authors.initials: R
authors.lastname: Lara
authors.affiliation: Departamento de Química-Centro de Síntesis Química de La Rioja (CISQ), Universidad de La Rioja, 26006, Logroño, Spain.
authors.forename: M Teresa
authors.initials: MT
authors.lastname: Moreno
authors.affiliation: Departamento de Química-Centro de Síntesis Química de La Rioja (CISQ), Universidad de La Rioja, 26006, Logroño, Spain.
authors.forename: Elena
authors.initials: E
authors.lastname: Lalinde
keywords: cyclometalating ligands; density functional calculations; luminescence; photochemistry; platinum