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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.

rsc advances

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