New discrete iodometallates with in situ generated triimidazole derivatives as countercations (Mn+ = Ag+, Pb2+, Bi3+)

Abstract

Through employing the solvothermal in situ N-alkylation of organic bases with alcohol molecules, four new iodometallates [L1]₂[Ag₈I₁₂]I₂ (L1³⁺ = 1,1′,1′′-(benzene-1,3,5)tris(3-methyl-1H-imidazol-3-ium)) 1, [L1]₂[Ag₆I₁₂] 2, [L1]₂[Pb₃I₁₂]·2H₂O 3, and [L1][Bi₂I₉] 4 were obtained. L1³⁺ originates from the in situ N-alkylation between 1,3,5-tri(1H-imidazol-1-yl)benzene (L2) and CH₃OH. X-ray single-crystal diffraction analysis reveals that all of the title compounds possess zero-dimensional (0D) structures. The octanuclear anionic cluster [Ag₈I₁₂]⁴⁻ of 1 possesses a sphere-like structure. An Ag₆I₆ unit with a hexagram structure occupies the equatorial position, while two AgI₄ tetrahedra (sharing point) occupy the axial positions. The anionic cluster, [Ag₆I₁₂]⁶⁻, of 2 exhibits a hexanuclear structure, which can be described as an aggregation of two incomplete cubanes (each lacking an Ag⁺ corner). The anionic cluster [Pb₃I₁₂]⁶⁻ of 3 can be described as an aggregation of three PbI₆ octahedra (sharing face), whereas two BiI₆ octahedra (also sharing face) aggregate to form a dinuclear cluster [Bi₂I₉]³⁻ of 4.