Construction of Cd/Zn(II)-1,2,4-Triazolate Coordination Complexes via Changing Substituents and Anions

A series of zero- to three-dimensional Cd/Zn(II)-1,2,4-triazolate coordination complexes have been obtained by changing the anions and the substituents on the triazole ring. Cd2(2-pytrz)2Cl4 (1) and Cd3(dpatrz)4Cl6 (2) (2-pytrz = 3,5-di(pyrid-2-yl)-1,2,4-triazole and dpatrz = 3,5-di(n-propyl)-4-amino- 1,2,4-triazole) have discrete binuclear and trinuclear structures, respectively. Cd3(atrz)4Cl6 (3) and Cd(atrz)2(SCN)2 (4) (atrz = 4-amino-1,2,4-triazole) are polymeric 1D chains constructed from trinuclear cadmium units and mononuclear cores. Cd(datrz)I (5), Zn(dmtrz)Cl (6), and Cd3(dmatrz)4(N3)6 (7) (datrz = 3,5-diamino-1,2,4-triazole, dmtrz = 3,5-dimethyl-1,2,4-triazole, and dmatrz = 3,5-dimethyl-4-amino-1,2,4-triazole) all show two-dimensional layer structures. Complexes 5 and 6 are 2D grids based on binuclear clusters and present (4.82)metal(4.82)trz topology. Complex 7 is of 2D (4,4) topology when trinuclear cadmium units are regarded as four-connected nodes. For complexes 17, weak hydrogen-bonding contacts link the discrete polynuclear clusters, 1D chains, or 2D layers to form three-dimensional supramolecular structures. Zn2(trz)3Cl (8) (trz = 1,2,4-triazole) presents an interesting 3D network based on three nonequivalent nodes and has a (46861224)(861254)(42841236)3 topology. Complexes 18 all exhibit strong blue fluorescence emission bands in the solid state at ambient temperature.