Anion-Templated Assembly of Multinuclear Copper(II)–Triazole Complexes

The reactions of [Cu(CH3CN)4]PF6 and Cu(ClO4)2 with ((1-benzyl-1H-1,2,3-triazol-4-yl)(pyridin-2-yl)phenylmethanol (Hpytm) in a 1:1 ratio under aerobic conditions afforded [Cu6(pytm)6(SiF6)](SiF6)2 (1) and {[Cu3(pytm)3(MeOH)(ClO4)](ClO4)2}n (2), respectively. Single-crystal X-ray crystallography reveals that both compounds contain the trinuclear, six-membered CuII cluster, [CuII3(μ2-κ3-N,O,N'-pytm)3]3+, as a building block. In 1, the two trinuclear clusters sandwich an SiF62– anion to form a discrete dimeric hexanuclear structure, whereas, in 2, the clusters are linked by ClO4– anions in a one-dimensional polymeric structure. Magnetic susceptibility measurements indicate that a relatively large antiferromagnetic coupling exists in each trinuclear cluster in 1 and 2, with the J values of –48.2(4) cm–1 and –69.2(2) cm–1, respectively. In addition, weak, yet non-negligible magnetic interactions between two Cu3II cluster units were observed for both complexes.