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

A series of new manganese thioarsenates(V) [Mn(en)2Cu(AsVS4)]n (1, en = ethylenediamine), [Mn(dien)2][Mn(dien)(AsVS4)]2 (2, dien = diethylenetriamine), [Mn(teta)(AsVS4)]n (3, teta = triethylenetetramine), and {[Mn(dap)2][Mn(dap)(AsVS4)]2}n (4, dap = 1,2-diaminopropane) have been solvothermally synthesized and structurally characterized. 1 displays a neutral heterometallic [Mn(en)2Cu(AsVS4)]n chain built up from the linkages of [Mn(en)2]2+ complexes and infinite heterometallic [Cu(AsVS4)2−]n chains, and represents the only example of incorporation of an unsaturated [Mn(en)2]2+ complex into the 1-D [Cu(AsVS4)2−]n framework. 2 consists of a discrete {[Mn(dien)]2(AsVS4)2}2− cluster and a charge compensating complex cation [Mn(dien)2]2+. 3 shows a 1-D neutral [Mn(teta)(AsVS4)]n chain constructed by the combination of both complex [Mn(teta)]2+ ions and tetrahedral [AsVS4]3− anions. 4 exhibits a rare 2-D {[Mn(dap)2][Mn(dap)(AsVS4)]2}n layer based on the linkages of [AsVS4]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 [AsVS4]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.