Solvothermal synthesis and characterization of two 2-D layered germanium thioantimonates with transition-metal complexes

Abstract

Two germanium thioantimonates [Co(dien)₂]₂GeSb₄S₁₀ (1, dien = diethylenetriamine) and [Mn(en)₃]GeSb₂S₆ (2, en = ethylenediamine) have been solvothermally synthesized and characterized by IR, UV/Vis, fluorescence spectroscopy, elemental analysis, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. 1 contains heterometallic pseudosemicube [GeSb₂S₇] clusters and chain-like Sb₄S₁₀ tetramers, which are interconnected to form a unique double layer of [GeSb₄S₁₀]⁴⁻ with 10-MR helical channels. 2 features a sheet layer of [GeSb₂S₆]²⁻ with ellipse-like 12-MR, where one [GeS₄] tetrahedra, one [SbS₃] trigonal-pyramid and one Ψ-[SbS₄] trigonal bipyramid are combined to form another heterometallic [GeSb₂S₈] cluster as a building unit. 1 and 2 exhibit absorption edges at 2.36 eV and 2.10 eV, respectively. 2 exhibits a fluorescence emission at room temperature.