Hydrazine-solvothermal methods to synthesize polymeric thioarsenates from one-dimensional chains to a three-dimensional framework

A series of polymeric Mn(ii)-thioarsenates [Mn(en)(3)](n)[(N(2)H(4))(2)Mn(6)(μ(6)-S)(μ-N(2)H(4))(2)(μ(3)-AsS(3))(4)](n) (1), [N(2)H(5)](n)[{Mn(μ-N(2)H(4))(2)(μ-AsS(4))}·0.5en](n) (2), [Mn(μ-trien){Mn(μ-N(2)H(4))(μ-AsS(3))}(2)](n) (3), [{Mn(N(2)H(4))}(2)(μ-N(2)H(4))(2){Mn(μ-N(2)H(4))(2)(μ-AsS(3))(2)}](n) (4), [Mn(3)(μ-N(2)H(4))(6)(μ(3)-AsS(4))(μ(2)-AsS(4))](n) (5), and [Mn(NH(3))(6)](n)[{Mn(NH(3))(μ-AsS(4))}(2)](n) (6) were synthesized using a hydrazine-solvothermal method. The thioarsenate units AsS(3) and AsS(4) coordinate to Mn(ii) ions with variable coordination modes, forming a Mn–As–S ternary cluster (1), chains (2, 4–6), and layers (3), respectively. The hydrazine molecules act as inter-cluster, intra-chain and intra-layer bridging ligands to join the Mn(ii) ions, resulting in hydrazine hybrid 1-D, 2-D, and 3-D Mn(ii)-thioarsenate moieties in 1–5. Compounds 1–6 exhibit tunable semiconducting band gaps varying in the range of 2.19–2.47 eV. Compound 1 displays stronger antiferromagnetic coupling interactions than that of compound 2.