Hydrothermal Synthesis and Characterization ofM2Te3O8(M=Mn, Co, Ni, Cu, Zn): A Series of Compounds with the Spiroffite Structure

Abstract

Several compounds isotypic to the mineral spiroffite were obtained as high quality single crystals via hydrothermal reactions. These materials, which have the general formulaM2Te3O8, crystallize in the monoclinic space groupC2/cand contain divalent transition metal ions and tellurite building blocks. Typical synthetic conditions for the preparation of these materials are 375°C for 3–5 days in an aqueous NH4Cl solution. This structure type is based on slabs containing Te2O6groups joined byMcations. These Te2O6groups are made up of two edge-sharing TeO3+1polyhedra. The metal tellurite slabs are connected to one another through tellurium(IV) atoms, which are coordinated by four oxygen atoms in a regular TeO4trigonal bipyramidal configuration. A detailed structural characterization via single crystal X-ray diffraction was performed on four compounds (Co2Te3O8:a=12.690(1) Å,b=5.211(2) Å,c=11.632(2) Å,β=98.98(1)°,V=759.7(3) Å3,R(Rw)=0.023 (0.046); Ni2Te3O8:a=12.407(1) Å,b=5.207(1)Å,c=11.509(1) Å,β=98.723(9)°,V=735.0(2) Å3,R(Rw)=0.025 (0.033); Cu2Te3O8:a=11.8368(8) Å,b=5.266(2) Å,c=12.2419(8) Å,β=100.316(6)°,V=750.7(2) Å3,R(Rw)=0.025 (0.032); Zn2Te3O8:a=12.681(2) Å,b=5.200(2) Å,c=11.786(2) Å,β=99.60(1)°,V=766.3(3) Å3,R(Rw)=0.031 (0.041)). The manganese analog (a=12.896(5) Å,b=5.398(2) Å,c=11.907(5) Å,β= 98.14(4)°) was identified via powder diffraction patterns. The cobalt, nickel, and copper compounds were observed to have an antiferromagnetic transition by DC magnetic susceptibility measurements. The band gaps were obtained by optical diffuse reflectance spectroscopy and show that these compounds are all wide band gap materials.