A Controlled Route to a Luminescent 3 d10 -5 d10 Sulfido Cluster Containing Unique AuCu2 (μ3 -S) Motifs

Alexander M Polgar; Chhatra B Khadka; Mahmood Azizpoor Fard; Brian Nikkel; Terrence O'Donnell; Tobias Neumann; Kiana Lahring; Kyle Thompson; Carolyn Cadogan; Florian Weigend; John F Corrigan

doi:10.1002/chem.201604880

A Controlled Route to a Luminescent 3 d¹⁰ -5 d¹⁰ Sulfido Cluster Containing Unique AuCu₂ (μ₃ -S) Motifs

Chemistry. 2016 Dec 19;22(51):18378-18382. doi: 10.1002/chem.201604880. Epub 2016 Nov 10.

Authors

Affiliations

¹ Department of Chemistry, The University of Western Ontario, London, Ontario, N6A 5B7, Canada.
² Department of Physics and Astronomy, The University of Western Ontario, London, Ontario, N6A 5B7, Canada.
³ Institut für Nanotechnologie, Karlsruher Institut für Technologie (KIT), Hermann-von Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany.
⁴ Institut für Physikalische Chemie, Karlsruher Institut für Technologie (KIT), Campus Süd, Fritz-Haber-Weg 2, 76131, Karlsruhe, Germany.
⁵ Centre for Advanced Materials and Biomaterials Research, The University of Western Ontario, London, Ontario, N6A 3K7, Canada.

PMID: 27778397
DOI: 10.1002/chem.201604880

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.

Keywords: chalcogens; cluster compounds; copper; gold; luminescence.