Solvothermal Synthesis And Properties Of Multinary Antimony Chalcogenides Containing Transition Metals Zinc Or Cadmium In The Multinary Amine System

In recent years,the research of chalcogenides has been favored by everyone,because of their rich structure and good properties,such as semiconductor,nonlinear optics,ion exchange,photoelectricity and magnetism and other fields of modern science and technology have a broad application prospect.Up to now,the methods of synthesizing chalcogenides mainly include solvothermal method,solid phase method,electrochemical method and fluxing method.In this paper,a series of multinary antimony chalcogenides containing zinc or cadmium were synthesized by solvothermal method in multinary amine system,and a series of properties of the compounds were studied.(1)Rb₂Zn Sb₄S₈(1)?[Zn(tren)₂H]Sb Se₄(2)and Ni₂(1,2-dap)₆Zn(1,2-dap)Sb₂Se₈(3)have been successfully synthesized in the multinary amine system.The results of single crystal X-ray diffraction show that compound 1belongs to triclinic crystal system,and the space group is P?1.Compound 1 is a two-dimensional layered structure consisting of[Zn Sb₄S₈]_n^2n-anion and Rb⁺cation.[Sb Zn S₅]_n^5n-chain is formed by alternating connection of pyramidal Sb S₃and tetrahedral Zn S₄units through shared angle,and three Sb S₃units form Sb₃S₃six-membered ring through shared angle connection.The[Sb Zn S₅]_n^5n-chain and Sb₃S₃six-membered ring form a[Zn Sb₄S₈]^2-ribbon structure by?₂-S atoms,[Zn Sb₄S₈]^2-ribbon are further connected by sharing?₂-S atoms to form a two-dimensional[Zn Sb₄S₈]^2n-layered structure,and the Rb⁺cations are located between the adjacent layers.Compound 2 belongs to monoclinic system with space group P2₁/n.Compound 2 is the zero-dimensional cluster consisting of[Sb Se₄]_n^3n-anion and[Zn(tren)₂H]³⁺complex.Here,the Zn²⁺ion is coordinated with four N atoms in a molecule of tris(2-aminoethyl)amine and one N atom in another tris(2-aminoethyl)amine to form the twisted trigonal-bipyramidal structure.The Sb atom and four Se atoms coordinate to form a tetrahedral structure Sb Se₄,the[Zn(tren)₂H]³⁺complex exists between[Sb Se₄]_n^3n-anions.Compound 3belongs to monoclinic system with space group P2₁/n.Compound 3 is the zero-dimensional cluster consisting of[Zn(1,2-dap)Sb₂Se₈]^4-anion and[Ni(1,2-dap)₃]²⁺complex.The[Ni(1,2-dap)₃]²⁺octahedral structure is formed by the coordination of the Ni²⁺ion with the six N atoms in the three molecule1,2-propylenediamine,the[Zn(1,2-dap)Se₂]^2-unit is formed by the coordination of Zn²⁺ion with two Se atoms and two N atoms in 1,2-propylenediamine of a molecule,the Sb⁵⁺ions coordinate with four Se atoms to form the tetrahedral structure Sb Se₄.The[Zn(1,2-dap)Sb₂Se₈]^4-anion cluster is formed by the connection of[Zn(1,2-dap)Se₂]^2-unit with two tetrahedral Sb Se₄through shared Se atoms,the[Ni(1,2-dap)₃]²⁺complex exists between[Zn(1,2-dap)Sb₂Se₈]^4-anions.The results of a series of analysis show that compounds 1-3 have semiconductor properties and photocurrent response characteristics,in which compound 3 has antiferromagnetism.(2)A kind of multinary antimony chalcogenide Rb₂Cd Sb S₃(SH)(4)containing transition metal cadmium was successfully synthesized in the mixed solvent of 1,2-propylenediamine and water.The results of single crystal X-ray diffraction show that compound 4 belongs to monoclinic system and its space group is P2₁/m.Compound 4 is a one-dimensional chains structure composed of[Cd Sb S₃(SH)]_n^2n-anion and Rb⁺cations.Among them,two pyramidal Sb S₃and two tetrahedral Cd S₄are connected to form[Cd₂Sb₂S₈(SH)₂]^4-eight-membered rings,and the adjacent eight-membered rings are further connected by sharing two S atoms to form a one-dimensional[Cd Sb S₃(SH)]_n^2n-anion chain,and Rb⁺cations exist between the chains.The results of solid state UV-Vis diffuse reflectance spectroscopy show that compound 4 has semiconductor properties.(3)A new antimony chalcogenide Cs₃Sb₅Se₉(5)was successfully synthesized in the mixed solvent of tetraethylenepentamine and water.The results of single crystal X-ray diffraction show that compound 5 belongs to triclinic crystal system and its space group is P?1.Compound 5 is a two-dimensional layered structure consisting of[Sb₅Se₉]_n^3n-anion and Cs⁺cations.Two octahedral Sb Se₆are connected by sharing?₃-Se atoms to form a dimer Sb₂Se₅,and the adjacent Sb₂Se₅dimer is connected by Se(8)-Se(9)and Se(10)-Se(11)bonds to form the[Sb₂Se₅]_n^4n-chain.The[Sb₃Se₅]^-ribbon is formed through the shared angle connection between[Sb₂Se₅]_n^4n-chain and the disordered trigonal Sb Se₃units interlaced up and down.Finally,these[Sb₃Se₅]^-ribbons are further interlinked with the dimer Sb₂Se₅by sharing?₃-Se atoms to form[Sb₅Se₉]_n^3n-anion layers,and Cs⁺cations exists between the layers.The results of solid state UV-Vis diffuse reflectance spectroscopy show that compound 5 has semiconductor properties.