Solvothermal Synthesis And Characterization Of Arsenic?Tin Chalcogenides With Transition Metal Complexes As Structure Directing Agent

In recent years,chalcogenides compounds have attracted much attention due to their variety of diverse structure types and potential application values,such as semiconductor,nonlinear optics,magnetism,ion exchange,photoelectric catalysis and molecular sieves.At present,solvothermal method has become the main method for the synthesis of chalcogenides compounds.In this article,multinary arsenic/tin chalcogenides compounds by different transition metals complexes as structure directing agent were synthesized in amine/amine-alcohol mixed organic solvents,and a series of characterization of the compounds were characterized.(1)In amine/amine-alcohol mixed solvent,by different transition metals complexes as structure directing agent were synthesized four new selenoarsenates[Co(tren)₂H]As Se₄(1),[TM₂(tren)₂][As₂Se₅](TM=Zn?Mn)(2?3)and[Ni₂(dien)₄][As₂Se₅](4)were synthesized.The X-ray diffraction results of single crystal show that compounds 1-4 were all zero-dimensional clusters structure.Compound 1 is composed of As Se₄tetrahedron and equilibrium cation[Co(tren)₂]²⁺;Compound 2 is formed by the dimer[As₂Se₅]^4-and the transition metal complex[Zn₂(tren)₂]⁴⁺,which is connected by Se atoms;In compound 3,there are two coordination modes of Mn²⁺,two octahedral[Mn(tren)]Se₂by shared edge connection forming to[Mn₂(tren)₂]Se₂cluster,[Mn₂(tren)]Se and[Mn₂(tren)₂]Se₂clusters by the dimer[As₂Se₅]^4-connection formed to the cluster structure of[Mn₂(tren)₂][As₂Se₅];Compound 4 is formed by consists of anion[As₄Se₆]^2-clusters and transition metal complex[Ni(dien)₂]²⁺.Meanwhile,compounds 1-4 were characterized by Powder X-ray Diffraction,Solid UV-visible Diffuse Reflection,Fluorescence Properties,Infrared Spectra Analysis,Thermogravimetric-Differential Thermal Analysis,Photocurrent Response and Electrocatalytic Oxygen Evolution Reaction.Among them,Fluorescence Analysis showed that compound 1-4 may have red emission characteristics;Compound 2 has the best photocurrent response and electrocatalytic oxygen evolution performance.(2)In diethylenetriamine(dien)and ethylene glycol mixed solvent,by different transition metals complexes as structure directing agent were synthesized three new stannates[Co(dien)₂]₂Sn₂Se₆(5),[TM(dien)₂]Sn S₃(TM=Co(6),Ni(7))were synthesized.The results of single crystal X-ray diffraction show that compounds 5,6 and 7 are isomorphic,belong to monoclinic system,P₂₁/n space group,and all of zero-dimensional cluster structure.The compound[Co(dien)₂]₂Sn₂Se₆(5)is formed by the cation[Co(dien)₂]²⁺and the dimer anion[Sn₂Se₆]^4-.The compounds 5-7were characterized by Powder X-ray Diffraction,Solid UV-visible Diffuse Reflection,Fluorescence Properties,Infrared Spectra Analyses,Thermogravimetric-Differential Scanning Calorimetry Analyses,Photocatalysis,Photocurrent Response and Electrocatalytic Oxygen Evolution Reaction.Among them,Fluorescence Analysis showed that compound 5 may have blue emission characteristics,compound 6 may have red emission characteristics;The results of photocatalytic activity test showed that compounds 5 and 6 had certain photodegradation activity.Compound 5 has the best photocurrent response and electrocatalytic oxygen evolution performance.(3)In ethylenediamine(en)and ethylene glycol mixed solvent,by two different transition metals complexes as structure directing agent were synthesized two new selenostannates[Ni_0.4Zn_0.6(en)₆]Sn₂Se₆(8)and[(Mn_1.67Zn_0.33)(en)₆]Sn₂Se₆(9)were synthesized.The results of single crystal X-ray diffraction show that compounds 8 and 9 are isomorphic,belong to orthogonal crystal system,Pbca space group,and all of zero-dimensional cluster structure.Compound 8 has consisting of the cation[Ni/Zn(en)₃]²⁺(where Ni and Zn are disordered and occupy 0.4and 0.6 space)and the dimer anion[Sn₂Se₆]^4-;Compound[(Mn_1.67Zn_0.33)(en)₆]Sn₂Se₆(9)is composed of cation[Mn/Zn(en)₃]²⁺and dimer anion[Sn₂Se₆]^4-(where Mn and Zn are disordered and occupy 1.67and 0.33 space).Compounds 8 and 9 were characterized by Powder X-ray Diffraction,Solid UV-visible Diffuse Reflection,Fluorescence Properties,Infrared Spectra,Thermogravimetric-Differential Scanning Calorimetry Analyses,Photocurrent Response and Electrocatalytic Oxygen Evolution Reaction.Among them,Fluorescence Analysis showed that compound 8 and 9 may have red emission characteristics;Compound8 has the best photocurrent response and electrocatalytic oxygen evolution performance.