Li6M(SeO3)4 (M = Co, Ni, and Cd) and Li2Zn(SeO3)2: Selenites with Late Transition-Metal Cations.

Abstract

A series of lithium metal selenites, Li6M(SeO3)4 (M = Co, Ni, and Cd) and Li2Zn(SeO3)2, were synthesized by hydrothermal and solid-state reactions. Li6M(SeO3)4 is composed of Li+ cations, MO6 octahedra, and SeO3 polyhedra, while Li2Zn(SeO3)2 consists of Li+, Zn(Li)O4 tetrahedra, and SeO3 polyhedra. Isostructural Li6Co(SeO3)4 and Li6Ni(SeO3)4 crystallize in the rhombohedral space group R3̅, forming a three-dimensional distorted cubic lattice. Li2Zn(SeO3)2 crystallizes in the orthorhombic space group Pbam and reveals a layered structure in the bc plane. Li6Cd(SeO3)4 revealing a unidimensional structure crystallizes in the polar non-centrosymmetric space group C2, attributed to the parallel alignment of distorted CdO6 octahedra. The direct-current magnetic susceptibility measurements unveil that Li6Co(SeO3)4 is a canted antiferromagnet with TN = 25 K, while Li6Ni(SeO3)4 undergoes an antiferromagnetic transition at TN = 54 K, having a negligible canted moment. The weak ferromagnetism observed in Li6Co(SeO3)4 indicates the significance of spin-orbit coupling, bringing about anisotropic exchange interactions. Li6Cd(SeO3)4 reveals a second harmonic generation (SHG) efficiency of 10 × α-SiO2. Dipole moment calculations on Li6Cd(SeO3)4 indicate that the cooperative interaction of CdO6 and SeO3 is responsible for the observed SHG properties. Band gaps of the compounds are enlarged as atomic number increases. The effect of late transition-metal cations with different coordination numbers on the framework structures and the subsequent physical properties will be also discussed.