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

Abstract

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. Cd 2 (2-pytrz) 2 Cl 4 ( 1 ) and Cd 3 (dpatrz) 4 Cl 6 ( 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. Cd 3 (atrz) 4 Cl 6 ( 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 Cd 3 (dmatrz) 4 (N 3 ) 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 (4.8 2 ) metal (4.8 2 ) trz topology. Complex 7 is of 2D (4,4) topology when trinuclear cadmium units are regarded as four-connected nodes. For complexes 1 − 7, weak hydrogen-bonding contacts link the discrete polynuclear clusters, 1D chains, or 2D layers to form three-dimensional supramolecular structures. Zn 2 (trz) 3 Cl ( 8 ) (trz = 1,2,4-triazole) presents an interesting 3D network based on three nonequivalent nodes and has a (4 6 8 6 12 24 )(8 6 12 54 )(4 2 8 4 12 36 ) 3 topology. Complexes 1 − 8 all exhibit strong blue fluorescence emission bands in the solid state at ambient temperature.