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Highly Luminescent Gold(I)–Silver(I) and Gold(I)–Copper(I) Chalcogenide Clusters
Author(s) -
Crespo Olga,
Gimeno M. Concepción,
Laguna Antonio,
Larraz Carmen,
Villacampa M. Dolores
Publication year - 2006
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200600566
Subject(s) - chemistry , phosphine , copper , luminescence , selenide , metal , chalcogenide , ligand (biochemistry) , crystallography , pyridine , silver sulfide , sulfide , chalcogen , stoichiometry , inorganic chemistry , selenium , polymer chemistry , medicinal chemistry , organic chemistry , materials science , optoelectronics , biochemistry , receptor , catalysis
The reactions of [AuClL] with Ag 2 O, where L represents the heterofunctional ligands PPh 2 py and PPh 2 CH 2 CH 2 py, give the trigoldoxonium complexes [O(AuL) 3 ]BF 4 . Treatment of these compounds with thio‐ or selenourea affords the triply bridging sulfide or selenide derivatives [E(AuL) 3 ]BF 4 (E=S, Se). These trinuclear species react with Ag(OTf) or [Cu(NCMe) 4 ]PF 6 to give different results, depending on the phosphine and the metal. The reactions of [E(AuPPh 2 py) 3 ]BF 4 with silver or copper salts give [E(AuPPh 2 py) 3 M] 2+ (E=O, S, Se; M=Ag, Cu) clusters that are highly luminescent. The silver complexes consist of tetrahedral Au 3 Ag clusters further bonded to another unit through aurophilic interactions, whereas in the copper species two coordination isomers with different metallophilic interactions were found. The first is analogous to the silver complexes and in the second, two [S(AuPPh 2 py) 3 ] + units bridge two copper atoms through one pyridine group in each unit. The reactions of [E(AuPPh 2 CH 2 CH 2 py) 3 ]BF 4 with silver and copper salts give complexes with [E(AuPPh 2 CH 2 CH 2 py) 3 M] 2+ stoichiometry (E=O, S, Se; M=Ag, Cu) with the metal bonded to the three nitrogen atoms in the absence of Au⋅⋅⋅M interactions. The luminescence of these clusters has been studied by varying the chalcogenide, the heterofunctional ligand, and the metal.