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)] [(NH)Mn(μ-S)(μ-NH)(μ-AsS)] (1), [NH] [{Mn(μ-NH)(μ-AsS)}·0.5en] (2), [Mn(μ-trien){Mn(μ-NH)(μ-AsS)}] (3), [{Mn(NH)}(μ-NH){Mn(μ-NH)(μ-AsS)}] (4), [Mn(μ-NH)(μ-AsS)(μ-AsS)] (5), and [Mn(NH)] [{Mn(NH)(μ-AsS)}] (6) were synthesized using a hydrazine-solvothermal method. The thioarsenate units AsS and AsS 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.