Spontaneous in situ generation of photoemissive aurophilic oligomers in water solution based on the 2-thiocytosine ligand

Abstract

Complexes [Au(S-2-thiocytosinate)(PMe₃)] (2, 2-thiocytosine = 4-amino-2-mercaptopyrimidine) and [Au(S-2-thiocytosine)(PMe₃)](CF₃CO₂) (3) have been prepared by the reaction of [Au(acac)(PMe₃)] (1, acac = acetylacetonate) or [Au(OCOCF₃)(PMe₃)] with 2-thiocytosine, respectively. The equimolecular mixture of complexes 1 and 3 also produces [{Au(PMe₃)}₂(μ-S,N¹-2-thiocytosinate)](CF₃CO₂) (4), which features two distinct [Au(PMe₃)]⁺ groups coordinated to the S and N¹ atoms of the heterocycle. Complex 4 experiences a ligand redistribution process in water solution that liberates [Au(PMe₃)₂](CF₃CO₂) and a brightly coloured and luminescent species of [Au_n(μ-S,N¹-2-thiocytosinate)_n] stoichiometry, presumably as a tetraauracycle (n = 4).