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Updated: Sep 23, 2025

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Hydrazine-solvothermal methods to synthesize polymeric thioarsenates from one-dimensional chains to a
Jingyu Han1, Shufen Li1, Chunying Tang2
1College of Chemistry, Chemical Engineering and Materials Science, Soochow University No. 199 Renai Road Suzhou 215123 P. R. China jiadingxian@suda.edu.cn.
Abstract:
A series of polymeric Mn(ii)-thioarsenates [Mn(en)3] [(N2H4)2Mn6(μ6-S)(μ-N2H4)2(μ3-AsS3)4] (1), [N2H5] [{Mn(μ-N2H4)2(μ-AsS4)}·0.5en] (2), [Mn(μ-trien){Mn(μ-N2H4)(μ-AsS3)}2] (3), [{Mn(N2H4)}2(μ-N2H4)2{Mn(μ-N2H4)2(μ-AsS3)2}] (4), [Mn3(μ-N2H4)6(μ3-AsS4)(μ2-AsS4)] (5), and [Mn(NH3)6] [{Mn(NH3)(μ-AsS4)}2] (6) were synthesized using a hydrazine-solvothermal method. The thioarsenate units AsS3 and AsS4 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.
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