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Double Photoinduced Jahn–Teller Distortion of Tetrahedral Au I Sn II Complexes
Author(s) -
Vilma Bojan R.,
LópezdeLuzuriaga José M.,
Monge Miguel,
Elena Olmos M.,
Echeverría Raquel,
Lehtonen Olli,
Sundholm Dage
Publication year - 2014
Publication title -
chempluschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.801
H-Index - 61
ISSN - 2192-6506
DOI - 10.1002/cplu.201300314
Subject(s) - chemistry , crystallography , molecular orbital , phosphine , oniom , tetrahydrothiophene , moiety , covalent bond , crystal structure , stereochemistry , molecule , biochemistry , organic chemistry , catalysis
Tetrahedral Au I complexes [ L 3 Au(SnCl 3 )] ( L =PMe 3 ( 1 ), PMe 2 Ph ( 2 ), PMePh 2 ( 3 ), and PPh 3 ( 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, [SnCl 3 ] − fragments covalently bonded to the corresponding [Au(PR 3 ) 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(PR 3 ) 3 ] + and [SnCl 3 ] − 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 AuP 3 + moiety is distorted leading to a T‐shape, whereas the SnCl 3 − unit is left almost unaltered. Molecular orbital and population analysis suggest that the emission of these tetrahedral Au I complexes arises from a 3 MC transition slightly perturbed by the SnCl 3 − fragment.