Supramolecular gold(I) compounds with trithiocyanuric acid: Self‐assembly and luminescent properties

[(N3S3)Au(AuPMe3)2]2 (1) and [(N3S3)Au(AuPEt3)2]2 (2) were prepared by treating AuCl(PMe3) or AuCl(PEt3) with H3N3S3 upon deprotonation by trimethylamine to give respective Au6 supermolecules. Using dppm(AuCl)2 instead of AuCl(PMe3) or AuCl(PEt3) to react with H3N3S3 in a similar reaction condition led to a rare heptanuclear supermolecule of [(N3S3)2Au7(dppm)4]Cl (3). It is noted that besides short intramolecular gold(I)⋯gold(I) distances, both compounds 1 and 2 also show intermolecular gold(I)⋯gold(I) distances of 3.067(1) and 3.241(1) Å, resulting in two‐dimensional and one‐dimensional polymeric gold(I) solid, respectively. In fact, compound 1 shows a similar two‐dimensional polymeric gold(I) solid to that of the reported [(N3S3)Au(AuPPhMe2)2]2 with an intermolecular gold(I)⋯gold(I) distance of 3.130(2) Å. Significantly, these intermolecular gold(I)⋯gold(I) distances are well correlated with their cone angles and emission energies. For example, intermolecular gold(I)⋯gold(I) distances increase in the order of 3.067(1) Å