A Controlled Route to a Luminescent 3 d10–5 d10 Sulfido Cluster Containing Unique AuCu2(μ3‐S) Motifs. Issue 51 (10th November 2016)

• Record Type: Journal Article
• Authors: Polgar, Alexander M.; Khadka, Chhatra B.; Azizpoor Fard, Mahmood; Nikkel, Brian; O'Donnell, Terrence; Neumann, Tobias; Lahring, Kiana; Thompson, Kyle; Cadogan, Carolyn; Weigend, Florian; Corrigan, John F.
• Is Part Of: Chemistry. Volume 22:Issue 51(2016)
• Page Start: 18378
• Page End: 18382
• Publication Date: 2016-11-10
• Subjects: chalcogens -- cluster compounds -- copper -- gold -- luminescence; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201604880
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The first examples of gold(I) trimethylsilylchalcogenolate complexes were synthesized and their reactivity showcased in the preparation of a novel gold–copper–sulfur cluster [Au4 Cu4 S4 (dppm)2 ] (dppm=bis(diphenylphosphino)methane). The unprecedented structural chemistry of this compound gives rise to interesting optoelectronic properties, including long‐lived orange luminescence in the solid state. Through time‐dependent density functional theory calculations, this emission is shown to originate from ligand‐to‐metal charge transfer facilitated by Au⋅⋅⋅Cu metallophilic bonding. Abstract : All that glitters is not (only!) gold : The triphenylphosphine‐ligated gold(I) trimethylsilylchalcogenolate complexes (Ph3 PAu‐ESiMe3 ; E = S, Se) were synthesized and their reactivity highlighted with the selective preparation of the gold–copper–sulfur cluster [Au4 Cu4 S4 (dppm)2 ] (dppm=bis(diphenylphosphino)methane). The cluster is comprised of [(μ3 ‐S)CuAu2 ] + units; the structural chemistry of this compound gives rise to interesting photophysical properties, including long‐lived orange luminescence in the solid state.