The Preparations,Structures And Properties Of Organic Hybrid Selenidogermanates And Selenidostannates

The diversified structures and excellent properties are the salient features of the Group14 metal sulfates and selenates.They can be used as functional materials in semiconductors,optoelectronics,and other fields.Therefore,in recent years,the study of Group 14 metal chalcogenides has attracted the research interests of scientists.Solvothermal method is an effective method to synthesize this type of compound.The use of different coordination capacities of ethylene polyamines with lanthanide metals and transition metals to form a coordination ion has become an effective method for synthesizing chalcogenides.In addition,by introducing thiophilic metals（Cu,Ag,Hg）,etc.,the structural and physicochemical properties of the Group 14 metal chalcogenide are enriched.In this paper,the solvothermal reaction systems of Sn/Se and Ge/Se were investigated.The transition metal and lanthanide metal complexes were used as the structure-directing agents to synthesize antimony and tin selenoacid salt compounds.And by changing the reaction conditions,the ternary Hg-Ge-Se was synthesized.1.Using peha,trien and tepa as solvents,the Ln/Sn/Se reaction system was studied and We synthesis of four new selenidostannates under solvothermal reaction conditions:[{La（peha）（Cl）}{La（peha）（NO₃）}（m-1κ²:2κ²-SnSe₄）]（1）,[H₂trien][{La（trien）₂}₂（m-1κ:2κ-Sn₂Se₆）][Sn₂Se₆]?H₂O（2）,and[{Ln（tepa）（m-OH）}₂（m-1κ:2κ-Sn₂Se₆）]_n·nH₂O（Ln=Sm（3）,Eu（4））.In the reaction system,peha,trien,and tepa are both solvents and ligands.Due to the different coordination number of ethylene polyamines,the coordination manner between seleno-stannate and lanthanide ions ism-1κ²:2κ²-SnSe₄,m-1κ:2κ-Sn₂Se₆.2.In the Ge/Se binary system,the compound[NH₄]₂[H₂N（CH₃）₂]₂Ge₂Se₆（5）was synthesizedusingaqueousdimethylaminesolution.Thecompounds[Ni（dien）₂]₂Ge₂Se₅（Se₂）（6）,[{Ni（tepa）}₂（m-Ge₂Se₆）]（7）,[Co（dien）₂]₂Ge₂Se₅（Se₂）（8）and[{Co（tepa）}₂（m-Ge₂Se₆）]（9）were prepared by dien and tepa coordination with transition metal Ni²⁺and Co²⁺.Due to the different ligands,dimeric discrete[Ge₂Se₇]^4–and[Ge₂Se₆]^4-and bridging anions[m-Ge₂Se₆]^4-with different structures were obtained.3.The Hg/Ge/Se ternary system was studied.The compound[H₂dien]HgGeSe₄（10）was synthesized using the organic amine dien as a solvent.In the reaction system,MnCl₂·4H₂O was added to synthesize transition metal-containing complex ions in different solvents:[Mn（dien）₂]HgGeSe₄（11）,[Mn（dien）₂]Hg₂GeSe₄（Se₂）（12）and[Mn（tepa）{HgGeSe3（Se2）}]（13）The compound 11-13 are the first synthesis of an Hg-Ge-Se ternary chalcogenide compound having a transition metal complex ion as a cation.The photocatalytic degradation activity of compounds 11 and 12 for CV and RhB,respectively,was studied.4.The structures of the synthesized compounds were determined by single crystal X-ray diffractometer.The composition of the compounds were characterized by elemental analysis and IR spectra.The optical properties and thermal stability of the compounds and the fluorescence properties of the lanthanide compounds were determined.