Control of aurophilic interaction: conformations and electronic structures of one-dimensional supramolecular architectures

Gold(I) chloride complexes with the diarsenic ligands cis-1,4-dihydro-1,4-diarsinines (cis-DHDAs) were synthesized. X-ray diffraction revealed that they formed one-dimensional polymeric structures through aurophilic interactions. Their higher-ordered structures are controlled by the ligand structure; methyl- and t-butyl substituted ligands offered transoid–transoid and transoid–cisoid conformations, respectively. Density functional theory (DFT) calculations indicated that the electronic structure of the aurophilic network was highly dependent on the conformations. This is the first study on the relationship between the chain conformation and 5d-orbital structures of gold complexes.