Synthesis and structures of two three-dimensional hybrid materials based on vanadium polyoxoanions and macrocyclic metal complexes

Abstract

The reactions of transition metal macrocyclic complexes [ML](ClO4)2 (L = 1,8-diethyl-1,3,6,8,10,13-hexaazacyclotetradecane, M=Ni, Cu) with NH4VO3 gave two coordination polymers, formulated as [NiL]3[VO3]6·0.5H2O (1) and [CuL]3[VO3]6·2H2O (2). Single-crystal X-ray diffraction analyses indicated that the central Ni(II)/Cu(II) atom achieves a distorted six-coordinate octahedral coordination geometry by the coordination of four nitrogen atoms from L, plus two oxygen atoms from [VO4] tetrahedra. Six [VO4] tetrahedra form a hexanuclear [V6O18]6− ring by sharing six μ2-oxygen atoms. The [NiL]2+ and [CuL]2+ moieties bridge the [V6O18]6− rings to form three-dimensional frameworks with one-dimensional hexagonal channels.