Syntheses and Structures of Three Hybrid Materials Using Vanadium Polyoxoanions and Macrocyclic Copper Complex as Building Blocks

The reactions of the four-coordinated macrocyclic copper complex [CuL](ClO4)(2) (L = 1,4,8,11-tetraazacyclotetradecane) with NH4VO3 under different conditions gave three inorganic-organic hybrid materials of [CuL][VO3](2)center dot 2.33H(2)O (1), [CuL](3)[V10O28]center dot 8H(2)O (2) and [CuL](3)[V6O18]center dot 8H(2)O (3). Single-crystal X-ray diffraction analyses reveal that three diverse vanadium polyoxoanions, [V6O18](6-) ring, [V10O28](6-) cluster, and [V12O35](10-) ring, were isolated from the same reactant NH4VO3 under different conditions. The [CuL](2+) bridges the [V10O28](6-) clusters to form a two-dimensional sheet in 2, and link the [V6O18](6-) rings in 1 and [V12O35](10-) rings in 3 into three-dimensional frameworks, respectively.