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

摘要

A series of new manganese thioarsenates(V) [Mn(en)(2)Cu((AsS4)-S-V)](n) (1, en = ethylenediamine), [Mn(dien)(2)]-[Mn(dien)((AsS4)-S-V)](2) (2, dien = diethylenetriamine), [Mn(teta)((AsS4)-S-V)](n) (3, teta = triethylenetetramine), and {[Mn(dap)(2)][Mn(dap)((AsS4)-S-V)](2)}(n) (4, dap = 1,2-diaminopropane) have been solvothermally synthesized and structurally characterized. 1 displays a neutral heterometallic [Mn(en)(2)Cu((AsS4)-S-V)](n) chain built up from the linkages of [Mn(en)(2)](2+) complexes and infinite heterometallic [Cu((AsS4)-S-V)(2-)](n) chains, and represents the only example of incorporation of an unsaturated [Mn(en)(2)](2+) complex into the 1-D [Cu((AsS4)-S-V)(2-)] n framework. 2 consists of a discrete {[Mn(dien)](2)((AsS4)-S-V)(2)}(2-) cluster and a charge compensating complex cation [Mn(dien)(2)](2+). 3 shows a 1-D neutral [Mn(teta)((AsS4)-S-V)](n) chain constructed by the combination of both complex [Mn(teta)] (2+) ions and tetrahedral [(AsS4)-S-V](3-) anions. 4 exhibits a rare 2-D {[Mn(dap)(2)][Mn(dap)-((AsS4)-S-V)](2)}(n) layer based on the linkages of [(AsS4)-S-V](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 [(AsS4)-S-V](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.