Double Photoinduced Jahn-Teller Distortion of Tetrahedral Au-I-Sn-II Complexes

作者：Vilma Bojan R; Lopez de Luzuriaga Jose M^*; Monge Miguel; Elena Olmos M; Echeverria Raquel; Lehtonen Olli; Sundholm Dage

来源：ChemPlusChem, 2014, 79(1): 67-76.

DOI：10.1002/cplu.201300314

Tetrahedral Au-I complexes [L,Au(SnCl3)] (L = PMe3 (1), PMe2Ph (2), PMePh2 (3), and PPh3 (4)) were prepared by treatment of the [(tht) Au(SnCl 3)] (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 red-shifted 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 (T-1) 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 (MC)-M-3 transition slightly perturbed by the SnCl3- fragment.

• 出版日期2014-1