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10.1002/chem.201404583
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Título: | Exploring Excited-State Tunability in Luminescent Tris-cyclometalated Platinum(IV) Complexes: Synthesis of Heteroleptic Derivatives and Computational Calculations |
Fecha de publicación: | 29-oct-2014 |
Cita bibliográfica: | Chemistry - A European Journal, 2014, 20, 17346-17359. |
ISSN: | 0947-6539 1521-3765 |
Materias relacionadas: | CDU::5 - Ciencias puras y naturales::54 - Química::546 - Química inorgánica |
Resumen: | The synthesis, structure, electrochemistry, and photophysical properties of a series of heteroleptic tris-cyclometalated Pt(IV) complexes are reported. The complexes mer-[Pt(C^N)2(C'^N')]OTf, with C^N = C-deprotonated 2-(2,4-difluorophenyl)pyridine (dfppy) or 2-phenylpyridine (ppy), and C'^N' = C-deprotonated 2-(2-thienyl)pyridine (thpy) or 1-phenylisoquinoline (piq), were obtained by reacting bis-cyclometalated precursors [Pt(C^N)2Cl2] with 2 equiv of AgOTf and an excess of the N'^C'H pro-ligand. The complex mer-[Pt(dfppy)2(ppy)]OTf was obtained analogously and photoisomerized to its fac counterpart. The new complexes display long-lived luminescence at room temperature in the blue to orange color range. The emitting states involve electronic transitions almost exclusively localized on the ligand with the lowest π-π* energy gap and have very little metal character. DFT and TD-DFT calculations on mer-[Pt(ppy)2(C'^N')]+ (C'^N' = thpy, piq) and mer/fac-[Pt(ppy)3]+ support this assignment and provide a basis for the understanding of the luminescence of tris-cyclometalated Pt(IV) complexes. Excited states of LMCT character may become thermally accessible from the emitting state in the mer isomers containing dfppy or ppy as chromophoric ligands, leading to strong nonradiative deactivation. This effect does not operate in the fac isomers or the mer complexes containing thpy or piq, for which nonradiative deactivation originates mainly from vibrational coupling to the ground state. |
Autor/es principal/es: | Juliá, Fabio Aullón, Gabriel Bautista, Delia González-Herrero, Pablo |
Facultad/Departamentos/Servicios: | Facultades, Departamentos, Servicios y Escuelas::Facultades de la UMU::Facultad de Química |
Versión del editor: | http://doi.wiley.com/10.1002/chem.201404583 |
URI: | http://hdl.handle.net/10201/101945 |
DOI: | 10.1002/chem.201404583 |
Tipo de documento: | info:eu-repo/semantics/article |
Número páginas / Extensión: | 15 |
Derechos: | info:eu-repo/semantics/openAccess Atribución-NoComercial-SinDerivadas 3.0 España |
Aparece en las colecciones: | Artículos: Química Inorgánica |
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Pt_Heteroleptic_Tris-cyclometalated.pdf | 7,81 MB | Adobe PDF | Visualizar/Abrir |
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