The Structural Diversity Triggered by Intermolecular Interactions between Au^IS₂ Groups: Aurophilia and Beyond

Abstract

The present study is aimed at elucidating the factors that direct the assembly of a specific family of AuI species. The assembly of AuI centers and dithiocarboxylato or xanthato ligands results in a surprising structural diversity observed by single‐crystal X‐ray diffraction. However, in solution, just evidences for discrete bimetallic [Au2L2] species have been observed. Interestingly, when dithiocarboxylato ligands have been used, a reversible supramolecular assembly has been observed forming the supramolecules of formulae [Au2L2]2 and [Au2L2]3. Initial studies on luminescent properties have been carried out at variable temperature. All the compounds show red emissions in the solid state at very similar energies, suggesting that the intramolecular interactions play a more relevant role in the luminescent properties than the intermolecular ones. The computational studies indicate that not only Au⋅⋅⋅Au interactions, but also Au⋅⋅⋅S and S⋅⋅⋅S ones play a role in the structure and energetic of the supramolecular species, as well as for the choice between supramolecular association or intramolecular oligomerization.

Organogold oligomers: exploiting iClick and aurophilic cluster formation to prepare solution stable Au4 repeating units

“…Recently, Lima et al reported the gold complex [Au{7-( prop-2-ine-1-yloxy)-1-benzopyran}(DAPTA)] (DAPTA = 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) which has a zigzag 1D chain selfassembled via aurophilic interactions. 41 In solution however, only a few oligomeric compounds featuring Au-Au linkages as the primary propagating backbone bond have been reported; [42][43][44][45][46][47][48][49][50] but they are either unstable at ambient temperature, or lack conclusive data supporting higher ordered structures. Common linkers include diphosphines, diacetylides and diisocyanides.…”

18-Membered Heterometallacyclic Gold(I) Compounds: Structural Influences of Co-crystallized Solvent

“…3.26 up to 3.28Å for 1a and from 3.25 to 3.34Å for 1b (with the shortest Au2· · ·S21 = 3.245(2)Å and the longest Au1· · ·S9 = 3.339(2)Å). These interactions are somewhat stronger than those observed for a monomeric gold(I) complex with a tribenzothiazolyl phosphine ligand (3.34 -3.46Å) [13] or the intermolecular Au· · ·S contacts responsible for the packing in discrete, bimetallic dithiocarboxylato complexes of Au(I) (3.43 -3.58Å) [14].…”

A hexanuclear gold carbonyl cluster

“…Recently, the effect of both aurophilic interactions and the nature of ancillary ligands on the self-assembly of complex molecular systems, as well as on the rich structural diversity found in the family of Au i thio-derivatives, has been studied in detail. 43 …”