Synthesis and Comparison of the Photophysical Properties of Anionic Diaryl [M(C^C)(CN)2]x− (M= AuIII, PtII) Complexes

Gomez de Segura, Iker Gil, Martin, Antonio, Bochmann, Manfred, Lalinde, Elena and Fernandez-Cestau, Julio (2026) Synthesis and Comparison of the Photophysical Properties of Anionic Diaryl [M(C^C)(CN)2]x− (M= AuIII, PtII) Complexes. Inorganic Chemistry. ISSN 0020-1669

Preview

PDF (Inorg. Chem 2026 ASAP) - Published Version Available under License Creative Commons Attribution. Download (5MB) | Preview

Abstract

The d8 complexes A[Au(C^C)(CN)₂] and A₂[Pt(C^C)(CN)₂] (where C^C = 4,4′-di-tert-butylbiphenyl-2,2′-diyl and A = NBu₄, K) were synthesized from [Au(C^C)Cl]₂ and [Pt(C^C)COD], which were themselves obtained from Sn(C^C)nBu₂. These complexes are bright photoemitters but exhibit remarkable differences in the origin of their photoluminescence. The tin complex Sn(C^C)nBu₂ displays blue/white photoluminescence originating from an admixture of ¹IL(C^C) and excimeric transitions. In contrast, the gold complexes exhibit green, long-lived phosphorescence (lifetimes up to 100 μs), which theoretical calculations attribute to ³IL(C^C) transitions. Although the platinum complexes show similar absorption and emission energies, theoretical calculations indicate an admixture with ³MLCT character in their emissive states. This is evidenced by: (i) luminescence lifetimes up to one order of magnitude shorter than those of the gold complexes under similar conditions; (ii) a greater contribution from ¹IL(C^C) fluorescence in solution, due to less efficient intersystem crossing (ISC); and (iii) reduced susceptibility to ³O₂ quenching, a consequence of the shorter triplet-state lifetime. The combination of water solubility, efficient ISC, and a long-lived triplet state with high sensitivity to dissolved O₂ endows K[Au(C^C)(CN)₂] with excellent catalytic activity in the photo-oxidation of p-bromothioanisole. This result underscores the potential of this class of Au(III) salts for photocatalysis in green solvents.

Item Type:	Article
Faculty \ School:	Faculty of Science > School of Chemistry, Pharmacy and Pharmacology
Depositing User:	LivePure Connector
Date Deposited:	21 May 2026 10:58
Last Modified:	21 May 2026 10:58
URI:	https://ueaeprints.uea.ac.uk/id/eprint/103127
DOI:	10.1021/acs.inorgchem.6c00495

Downloads

Actions (login required)

View Item