Solvothermal Synthesis And Properties Of Main Group Metal Chalcogenides With Complex Cations

The main group metal chalcogenides are a kind of materials with novel structure and excellent properties.These materials have potential application in the fields of magnetism,nonlinear optics,catalysis,ion exchange,semiconductor and the others.The introduction of transition metals into the framework of main group metal chalcogenides might result in the richer structures and more unique properties,which has aroused great interest in the research of the main group metal chalcogenides.In this paper,15 main group metal chalcogenides were obtained by solvothermal synthesis method.These compounds were characterized by X-ray single crystal diffraction,elemental analysis,X-ray powder diffraction,infrared spectrum and ultraviolet spectrum.The optical,magnetic and photoelectronic properties of some compounds were also discussed.Chalcogenidoantimonates containing vanadium complex cations:A series of new vanadium???chalcogenidoantimonates[V^??dap?₂SbQ₃]?Q=S?1?,Se?2?;dap=1,2-diaminopropane?,[H₂dien][V₂^??en?₂?dien?₂??₂-O?][SbSe₄]₂?3,en=ethylenediamine;dien=diethylenetriamine?and[V^??dien?₂SbSe₄]?4?have been solvothermally synthesized and structurally characterized.Both 1 and 2 contain neutral vanadium???-centered complexes[V^??dap?₂SbQ₃],where the[SbQ₃]^3-anion acts as a chelating ligand to complex[V^??dap?₂]³⁺,but they exhibit different molecular conformation.3 consists of selenidoantimonate anions[SbSe₄]^3-,protonated H₂dien²⁺cation,and dinuclear complex[V₂^??en?₂?dien?₂??₂-O?]⁴⁺based on two[V^??en??dien?]³⁺units bridged by one?₂-O group.4 contain neutral[V^??dien?₂SbSe₄]moieties with seven coordinated vanadium centre,which offers the rare example of high coordination of nitro-selenidovanadium???complex,mainly because vanadium???ion has regular octahedral configuration based on the structures in the solid state.The optical,magnetic and photoelectronic properties of all compounds have been investigated,and density functional theory calculation of 4 has also been studied.Selenidostannates containing transition metal complex cations:A series of new hybrid selenidostannates[Mn?en?₂?hda?]₂[Sn₂Se₆]?5,en=ethylenediamine,hda=N-?2-Hydroxyethyl?ethylenediamine?,[Ni?teta??en?][Ni?teta??hda?][Sn₄Se₁₀]?6,teta=triethylenetetramine?,[Mn?hda?₂]_n[SnMnSe₄]_n?7?,[Mn?dien?₂]_n-[SnMnSe₄]_n?8,dien=diethylenetriamine?,and[Zn₂?en?₂??₄-SnSe₄?]_n?9?were solvothermally synthesized in hda solvent and structurally characterized.5 is composed of discrete[Sn₂Se₆]^4-anion and complex[Mn?en?₂?hda?]²⁺cation as counterion.6 contains[Ni?teta??en?]²⁺ion,[Ni?teta??hda?]²⁺ion and[Sn₄S₁₀]^4-adamantane-like ion built from corner-sharing connection of four[SnSe₄]^4-tetrahedra,which offers the rare example of hybrid selenidostannate combined with two different types of transition metal complexes as counterions.Both 7 and 8 contain 1-D heterometallic[SnMnSe₄^2-]_n anionic chain constructed by[Sn/MnSe₄]tetrahedra sharing opposite edges,whose Sn⁴⁺and Mn²⁺ions are situated at the same site in the lattice,but their chains exhibit two different configurations.9 exhibits a new type of2-D organic-decorated[Zn₂?en?₂??₄-SnSe₄?]_n layer incorporating rare tetrahedral[ZnSe₂?en?]complexes.Their optical and photocurrent response properties were studied,and density functional theory calculation for 9 was also performed.Chalcogenidogermanates containing transition metal complex cation:A series of newhybridchalcogenogermanates[V₂?en?₆??-O?]-[Ge₂Se₆]?10?[V?en?₂?ea?]₂[Ge₂Se₆]?11,Hea=ethanolamine?,[V?teta??ea?]₂[Ge₂Se₆]?12,teta=triethylenetetramine?,[[Mn₂?en?₄Ge₂S₆]_n?13,en=ethylenediamine?,[Mn₂?dap?₄-Ge₂S₆]_n?15,dap=1,2-diaminopropane?,[H₂dien]_n[MnGeS₄]_n?14,dien=diethylenetriamine?were solvothermally synthesized and structurally characterized.10 is composed of[Ge₂Se₆]^4-anion and dinuclear complex cation[V₂?en?₆??-O?]⁴⁺containing en molecule as rare monodentate ligand.Both 11and 12 consist of[Ge₂Se₆]^4-anions constructed by two[GeSe₄]tetrahedra sharingacommonedgeanddiscretecomplexcations[V?en?₂?ea?]²⁺/[V?teta??ea?]²⁺.Both 13 and 15 contain dimeric[Ge₂S₆]^4-anions and[Mn?en?₂]²⁺/[Mn?dap?₂]²⁺complex cations,which are interconnected to generate1-D neutral chain-like structures[Mn₂?en?₄Ge₂S₆]_n and[Mn₂?dap?₄Ge₂S₆]_n,respectively.14 consists of protonated H₂dien²⁺cation and 1-D straight chain built from[MnS₄]and[GeS₄]tetrahedra sharing opposite edges,which offers the only example of chelating amine uncoordinated to transition metal ion.Although some selenidogermanates with transition metal complexes have been successfully prepared,no selenidogermanates with trivalent vanadium complexes are documented.Therefore,10-12 offer the first examples of selenidogermanates with trivalent vanadium complexes under solvothermal conditions.Their optical and photocurrent response properties were studied,and density functional theory calculations of 11 is also performed.