Discrete Singular Metallophilic Interaction in Stable Large 12-Membered Binuclear Silver and Gold Metallamacrocycles of Amido-Functionalized Imidazole and 1,2,4-Triazole-Derived N-Heterocyclic Carbenes

[Image: see text] Metallophilic interactions were observed in four pairs of 12-membered metallamacrocyclic silver and gold complexes of imidazole-derived N-heterocyclic carbenes (NHCs), [1-(R(1))-3-N-(2,6-di-(R(2))-phenylacetamido)-imidazol-2-ylidene](2)M(2) [R(1) = p-MeC(6)H(4), R(2) = Me, M = Ag (1b) and Au (1c); R(1) = Me, R(2) = i-Pr, M = Ag (2b) and Au (2c); R(1) = Et, R(2) = i-Pr, M = Ag (3b) and Au (3c)], and a 1,2,4-triazole-derived N-heterocyclic carbene (NHC), [1-(i-Pr)-4-N-(2,6-di-(i-Pr)-phenylacetamido)-1,2,4-triazol-2-ylidene](2)M(2) [M = Ag (4b) and Au (4c)]. The X-ray diffraction, photoluminescence, and computational studies indicate the presence of metallophilic interactions in these complexes, which are significantly influenced by the sterics and the electronics of the N-amido substituents of the NHC ligands. The argentophilic interaction in the silver 1b–4b complexes was stronger than the aurophilic interaction in the gold 1c–4c complexes, with the metallophilic interaction decreasing in the order 4b > 1b > 1c > 4c > 3b > 3c > 2b > 2c. The 1b–4b complexes were synthesized from the corresponding amido-functionalized imidazolium chloride 1a–3a and the 1,2,4-triazolium chloride 4a salts upon treatment with Ag(2)O. The reaction of 1b–4b complexes with (Me(2)S)AuCl gave the gold 1c–4c complexes.