Double photoinduced jahn-teller distortion of tetrahedral Au I-SnII complexes

  1. Bojan, R.V. 1
  2. Lopez-De-Luzuriaga, J.M. 1
  3. Monge, M. 1
  4. Olmos, M.E. 1
  5. Echeverria, R. 1
  6. Lehtonen, O. 2
  7. Sundholm, D. 2
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 University of Helsinki
    info

    University of Helsinki

    Helsinki, Finlandia

    ROR https://ror.org/040af2s02

Revue:
ChemPlusChem

ISSN: 2192-6506

Année de publication: 2014

Volumen: 79

Número: 1

Pages: 67-76

Type: Article

beta Ver similares en nube de resultados
DOI: 10.1002/CPLU.201300314 SCOPUS: 2-s2.0-84893229872 WoS: WOS:000337974900008 GOOGLE SCHOLAR lock_openAccès ouvert editor

D'autres publications dans: ChemPlusChem

Résumé

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.