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

摘要

The reactions of the four-coordinated macrocyclic copper complex [CuL](ClO_4)_2(L = 1,4,8,11-tetraazacyclotetradecane) with NH_4VO_3 under different conditions gave three inorganic-organic hybrid materials of [CuL][VO_3]_2·2.33H_2O(1), [CuL]_3[V_(10)O_(28)]·8H_2O(2) and [Cu L]3[V_6O_(18)]·8H_2O(3). Single-crystal X-ray diffraction analyses reveal that three diverse vanadium polyoxoanions, [V_6O_(18)]6- ring, [V_(10)O_(28)]6- cluster, and [V_(12)O_(35)]^(10-) ring, were isolated from the same reactant NH_4VO_3 under different conditions. The [CuL]^(2+) bridges the [V10O28]6- clusters to form a two-dimensional sheet in 2, and link the [V_6O_(18)]^(6-) rings in 1 and [V_(12)O_(35)]^(10-) rings in 3 into three-dimensional frameworks, respectively.