Synthesis and crystal structures of two three-dimensional vanadium polyoxoanion-bridged macrocyclic metal complexes

The reactions of transition metal macrocyclic complexes ML](ClO₄)₂ (L?=?5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, M?=?Ni, Cu) with NH₄VO₃ under hydrothermal conditions gave two coordination polymers, namely NiL]₂V₆O₁₇] and CuL]₂V₆O₁₇]. Single-crystal X-ray diffraction analyses indicated that the central Ni(II)/Cu(II) atom displays a distorted six-coordinate octahedral coordination geometry by coordination with four nitrogen atoms of L, and two oxygen atoms of VO₄] tetrahedrons. Compounds NiL]₂V₆O₁₇] and CuL]₂V₆O₁₇] show three-dimensional structures, which are constructed through the connections of dodecanuclear V₁₂O₃₂]^4? rings with NiL]²⁺ in NiL]₂V₆O₁₇], and V₈O₂₂] _n ^4n? chains with CuL]²⁺ in CuL]₂V₆O₁₇], respectively, generating one-dimensional channels.