Double photoinduced jahn-teller distortion of tetrahedral Au I-SnII complexes
- Bojan, R.V. 1
- Lopez-De-Luzuriaga, J.M. 1
- Monge, M. 1
- Olmos, M.E. 1
- Echeverria, R. 1
- Lehtonen, O. 2
- Sundholm, D. 2
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1
Universidad de La Rioja
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2
University of Helsinki
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ISSN: 2192-6506
Año de publicación: 2014
Volumen: 79
Número: 1
Páginas: 67-76
Tipo: Artículo
beta Ver similares en nube de resultadosOtras publicaciones en: ChemPlusChem
Resumen
Tetrahedral AuI complexes [L3Au(SnCl3)] (L=PMe3 (1), PMe2Ph (2), PMePh2 (3), and PPh3 (4)) were prepared by treatment of the [(tht)Au(SnCl3)] (tht=tetrahydrothiophene) complex with three equivalents of the corresponding tertiary phosphine. The crystal structures of complexes 1-4 have been determined through X-ray diffraction studies showing, in all cases, [SnCl3] fragments covalently bonded to the corresponding [Au(PR3)3]+ units, which leads to a tetrahedral coordination environment for gold. Complexes 3 and 4 show phosphorescence in the solid state at room temperature and 77 K that is largely redshifted relative to the free [Au(PR3)3]+ and [SnCl3] counterparts. Correlated MP2, SCS-MP2, and ONIOM MP2/UFF calculations suggest a largely distorted lower triplet excited state (T1) for each model system. The AuP3 + moiety is distorted leading to a T-shape, whereas the SnCl3 unit is left almost unaltered. Molecular orbital and population analysis suggest that the emission of these tetrahedral AuI complexes arises from a 3MC transition slightly perturbed by the SnCl3 - fragment. © 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.