A series of new manganese thioarsenates(v) based on different unsaturated [Mn(amine)x]2+ complexes

Abstract

A series of new manganese thioarsenates(V) [Mn(en)₂Cu(As^VS₄)]_n (1, en = ethylenediamine), [Mn(dien)₂][Mn(dien)(As^VS₄)]₂ (2, dien = diethylenetriamine), [Mn(teta)(As^VS₄)]_n (3, teta = triethylenetetramine), and {[Mn(dap)₂][Mn(dap)(As^VS₄)]₂}_n (4, dap = 1,2-diaminopropane) have been solvothermally synthesized and structurally characterized. 1 displays a neutral heterometallic [Mn(en)₂Cu(As^VS₄)]_n chain built up from the linkages of [Mn(en)₂]²⁺ complexes and infinite heterometallic [Cu(As^VS₄)²⁻]_n chains, and represents the only example of incorporation of an unsaturated [Mn(en)₂]²⁺ complex into the 1-D [Cu(As^VS₄)²⁻]_n framework. 2 consists of a discrete {[Mn(dien)]₂(As^VS₄)₂}²⁻ cluster and a charge compensating complex cation [Mn(dien)₂]²⁺. 3 shows a 1-D neutral [Mn(teta)(As^VS₄)]_n chain constructed by the combination of both complex [Mn(teta)]²⁺ ions and tetrahedral [As^VS₄]³⁻ anions. 4 exhibits a rare 2-D {[Mn(dap)₂][Mn(dap)(As^VS₄)]₂}_n layer based on the linkages of [As^VS₄]³⁻ anions and [Mn(dap)_x]²⁺ (x = 1, 2) groups. These results show that different unsaturated [Mn(amine)_x]²⁺ complexes are directly bonded to [As^VS₄]³⁻ anions to give different manganese thioarsenates(V), which have a significant structure directing effect on the structures of manganese thioarsenates(V) under similar solvothermal conditions. The present compounds exhibit wide-band-gap semiconducting properties with absorption band edges between 2.00 and 2.58 eV, and density functional theory calculations for compounds 1, 3 and 4 have also been performed.