Double Photoinduced Jahn–Teller Distortion of Tetrahedral AuI[BOND]SnII Complexes

Authors

  • Dr. R. Vilma Bojan,

    1. Departamento de Química, Universidad de la Rioja, Centro de Investigación en Síntesis Química (CISQ), Complejo Científico Tecnológico, 26004 Logroño (Spain), Fax: (+34) 941299621
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  • Prof. Dr. José M. López-de-Luzuriaga,

    Corresponding author
    1. Departamento de Química, Universidad de la Rioja, Centro de Investigación en Síntesis Química (CISQ), Complejo Científico Tecnológico, 26004 Logroño (Spain), Fax: (+34) 941299621
    • Departamento de Química, Universidad de la Rioja, Centro de Investigación en Síntesis Química (CISQ), Complejo Científico Tecnológico, 26004 Logroño (Spain), Fax: (+34) 941299621

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  • Dr. Miguel Monge,

    1. Departamento de Química, Universidad de la Rioja, Centro de Investigación en Síntesis Química (CISQ), Complejo Científico Tecnológico, 26004 Logroño (Spain), Fax: (+34) 941299621
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  • Dr. M. Elena Olmos,

    1. Departamento de Química, Universidad de la Rioja, Centro de Investigación en Síntesis Química (CISQ), Complejo Científico Tecnológico, 26004 Logroño (Spain), Fax: (+34) 941299621
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  • Raquel Echeverría,

    1. Departamento de Química, Universidad de la Rioja, Centro de Investigación en Síntesis Química (CISQ), Complejo Científico Tecnológico, 26004 Logroño (Spain), Fax: (+34) 941299621
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  • Dr. Olli Lehtonen,

    1. Department of Chemistry, P.O. Box 55 (A.I. Virtanens plats 1), FIN-00014 University of Helsinki (Finland)
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  • Prof. Dr. Dage Sundholm

    1. Department of Chemistry, P.O. Box 55 (A.I. Virtanens plats 1), FIN-00014 University of Helsinki (Finland)
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Abstract

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 14 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.

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