ZnVSe2O7 and Cd6V2Se5O21:: New d10 transition-metal selenites with V(IV) or V(V) cations

Two new metal selenites with a combination of vanadium(IV) or vanadium(V) cations, namely, ZnVSe2O7 and Cd6V2Se5O21, have been synthesized by hydrothermal and high-temperature solid-state reactions, respectively. The structure of ZnVSe2O7 features a 3D network of vanadium(IV) selenite with ID tunnels occupied by zinc(II) ions. The 3D network of vanadium(IV) selenite is formed by corner-sharing (VO6)-O-IV octahedral chains bridged by selenite groups. In Cd6V2Se5O21, the interconnection of cadmium(II) ions by bridging and chelating selenite groups led to a 3D framework with large tunnels along the b axis, and the 1D chains of corner-sharing (VO4)-O-V tetrahedra are inserted in the above large tunnels and are bonded to the cadmium selenite framework via Cd-O-V bridges. Both compounds exhibit broad emission bands in the blue-light region. Results of magnetic property measurements show there is significant antiferromagnetic interaction between V4+ centers in ZnVSe2O7. The electronic structure calculations for both compounds have been also performed.