Syntheses,Structure,and Properties Of Novel Quaternary Sulfides

Multinary metal sulfides have received widespread attention because of their structural diversity and their excellent performance.In the past ten years,the rapid development of quaternary sulfides has greatly enriched the structure and properties of sulfides.One of the common synthetic strategies for new metal sulfides is to introduce late transition metals into ternary sulfides.However,transition metals are prone to form binary sulfide precipitates and are difficult to participate in the construction of the polysulfide framework under solvothermal conditions.We solve this problem by introducing mineralizers and late transition metal ions to form soluble complexes.In this paper,thiophenol is used as a mineralizer to synthesize a series of mercury-containing quaternary metal sulfides under mild solvothermal conditions,the crystal structure,optical and electrical properties are studied.The research contents are as follows:1.Two novel quaternary antimony sulfides Rb₂Hg Sb S₃(SH)(1)and Cs₂Hg Sb S₃(SH)(2)were synthesized under solvothermal conditions by using thiophenol as a mineralizer and using alkali metal ions Rb⁺,Cs⁺as structure-directing agents.And the two compounds have the same structure.Two Hg S₄ tetrahedra and two Sb S₃ trigonal pyramids are corner-shared to form an eight-membered ring[Hg₂Sb₂S₆(SH)₂]^4-,which extend infinitely to form a one-dimensional chain by share S atoms,and alkali metal ions are located between the chains.The XRD patterns show that both compounds 1 and 2 are pure phases.And the UV-vis diffuse-reflectance patterns show that both 1 and 2 have semiconductor properties.The photoelectric performance test on them shows that compounds 1 and 2 have good photoelectric response performance.2.Three novel quaternary arsenic sulfides Rb₂Hg As S₃(SH)(3),Cs Hg As S₃(4),and KHg As S₃(5)with different structures were synthesized under the solvothermal conditions by using alkali metal ions Rb⁺,Cs⁺,K⁺as structure-directing agents and using thiophenol as a mineralizer.Among them,compound 3 and compounds 1,2 are of the same structure,all of them are one-dimensional chain structures containing-SH groups,and show very good photoelectric response performance.Compound 4 features a two-dimensional layered structure.Hg S₄ tetrahedra are connected by sharing S atoms to form[Hg S₃]_n^4n-helical chains,and adjacent[Hg S₃]_n^4n-chains are connected by As S₃ units to form a two-dimensional[Hg₂As₂S₆]_n^2n-anions layer.Cs⁺ions are located between the layers.The XRD patterns show that compounds 3 and 4 are both pure phases.And the UV-vis diffuse-reflectance patterns show that both 3 and 4 have semiconductor properties.Compound 5 also features a layered structure.Hg S₄ tetrahedra connect with four adjacent As S₃ trigonal pyramids by sharing S atoms,and it extends infinitely to form a two-dimensional[Hg₂As₂S₆]_n^2n-anion layer with eight-membered rings[Hg₂As₂S₄]and six-membered rings[Hg₂As S₃].K⁺ions are located between the layers.