Journal
DALTON TRANSACTIONS
Volume 45, Issue 26, Pages 10599-10608Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c6dt01722c
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Funding
- Ministerio de Economia y Competitividad, Spain [CTQ2015-69568-P]
- Ministerio de Educacion, Cultura y Deporte, Spain (FPU grant)
- Fundacion Seneca [19890/GERM/15]
- Universidad de Murcia
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The synthesis, electrochemistry and photophysical properties of a family of Pt(IV) complexes with cyclo-metalated 2-(9,9-dimethylfluoren-2-yl)pyridine (flpy) are reported. Homoleptic and heteroleptic tris-cyclometalated complexes with a meridional configuration, mer-[Pt(C<^>N)(2)(flpy)]OTf, with C<^>N = flpy or cyclometalated 2-phenylpyridine (ppy), were prepared by reacting the bis-cyclometalated precursors [Pt(C<^>N)(2)Cl-2] with flpyH in the presence of two equivalents of AgOTf. The corresponding facial isomers were obtained by photoisomerization. The Pt(IV) complexes with flpy display intense absorptions in the near-visible region and yellow phosphorescence in fluid solutions at 298 K, with quantum yields in the range 0.06-0.28 and lifetimes of hundreds of microseconds. The emissions arise from essentially (LC)-L-3 (flpy) states in all cases, with little metal-orbital contribution. However, computational calculations and experimental data demonstrate that subtle variations in the contribution of metal orbitals to the emitting state have a profound impact on quantum yields, while nonradiative deactivation through the thermal population of deactivating LMCT states does not have a significant influence.
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