Syntheses And Properties Of Novel Chalcogenidometalate Clusters Containing Indium And Tin

In recent years,chalcogenide clusters containing indium and tin have attracted much attention due to their good applications in photoluminescence,nonlinear optics,photoelectrocatalysis,ion selective exchange,gas adsorption separation and so on.Upto now,the structure types of such materials are relatively limited and the research on their properties is relatively inadequate.Metal chalcogenide clusters with novel structures and unique functions have become the hotspot and focus of inorganic synthetic chemistry.The synthesis of metal chalcogenide clusters is mainly limited to the raw materials by using inorganic salts or their simple materials and sulfur under medium-temperature solvothermal method(the reaction temperature is generally higher than 150°C)which organic amines are the main solvent.By selecting a suitable precursor,the reaction temperature can be greatly reduced,which can not only reduce energy consumption but also synthesize crystal phases that cannot be obtained at conventional temperatures.Based on this,in this paper,several examples of indium-sulfur clusters and tin-sulfur clusters with novel structures were successfully constructed by using organic metals as precursors.The specific researches are as follows:(1)Indium acetylacetonate was used as the source of indium,and the first case of zero-Dimensional(0D)double T3 indium sulfur cluster dimer{(T3)₂-In₂₀S₃₃}was constructed under the conditions of 1,5-diazabicyclo[4.3.0]non-5-ene and1,3-propanediamine as the solvent and the template agent.The study found that the synthesis time has a great effect on the degree of cross-linking between indium chalcogenide clusters.Under the same reaction conditions,one-dimensional(1D)T3indium sulfur cluster chains{(T3-In₁₀S₁₇)n}and three-dimensional(3D)framework{(T3-In₁₀S₁₈)_n}based on T3 type indium sulfur cluster can be obtained by extending the reaction time.The study also found that the cross-linked dimension(0D/1D/3D)has a great impact on the bandwidth and photoelectric response of the indium-sulfur cluster aggregates.(2)Using butyltin as the tin source,three cases of tin chalcogenide rings({R9-(butyl Sn)₉S₁₂(ox)₃},{R11-(butyl Sn)₁₁S₁₄(ox)₄},{R12-(butyl Sn)₁₂S₁₆(ox)₄}(ox stands for oxalic acid))with different sizes were obtained in the solvothermal system of ethylene glycol and organic amines(N-methylpiperazine,pentamethyldiethylenetriamine,and morpholine,respectively).and realized in situ oxygen doping of tin chalcogenide rings.It was found that the size of tin-sulfur cluster rings greatly affects their fluorescence emission peaks and intensities.(3)Butyltin was used as the tin source,and second metals(respectively,manganese acetate and nickel acetate)were selected.Two cases of ribbon-shaped metal complex-terminated isolated tetranuclear butyltin chalcogenide clusters{butyl Sn)₄S₈M₂(TEPA)₂}(M=Mn,Ni)were synthesized under the conditions of alcohol or hydrothermal containing tetraethylenepentamine(TEPA).The study found that both compounds have obvious ferromagnetic behavior.The researches in this paper have verified that organometals can be used as precursors to synthesize metal chalcogenide clusters in solvothermal systems containing organic amines.This can reduce the reaction temperature to 120°C or even 80°C,and has obtained several novel structure which can not get by using inorganic salts or elemental metals.This provides some reference for the synthesis of metal chalcogenide cluster systems.