Study On Solvothermal Synthesis And Properties Of Inorganic-Organic Hybrid Chalcogenidoantimonates And Chalcogenidostannates

The Main Group chalcogenidometalates compounds have attract much attention in recent years due to the applications in catalysis,ion exchange,photoelectric materials,semiconductor materials and rich structures.In this paper,twelve novel compounds were synthesized by introducing transition metal ions(TM2+)into Sb/S and Sn/Se systems under hydrazine-solvothermal or hydrothermal conditions.The main research contents of this paper are:1.1.Under hydrazine-solvothermal conditions,eight TM-containing thioantimonates were synthesized by changing the second solvent or ligand,the thioantimonates including[Mn(NH3)6]2[{Mn(NH3)3}2(?3-SbS4)2]Cl2(1),[Mn(NH3)6][{Mn(NH3)4}2(?-SbS4)2]·2H2O(TM=Mn(2),Fe(3)),[Mn(NH3)6][{Mn2(?-SbS4)2}(?-N2H4)2](4),[{Mn(N2H4)}2{Mn(?-SbS3)2(?-N2H4)2}(?-N2H4)2]n(5),[Hen]2[TM5(N2H4)6(Sb2S5)3](TM=Mn(6),Fe(7))and[(CH3)2NH2]CuSb4S7(8).In compound 1,the SbS4 tetrahedron joins the[Mn(NH3)4]2+ unit into a two-dimensional[{Mn(NH3)3}2(?-SbS4)2]2-anion through three S in the coordination mode of ?3-SbS4.In compounds 2 and 3,the SbS4 unit acts as a monodentate bridging ligand to connect two[Mn(NH3)4]2+ units to form a[{Mn(MH3)4}2(?-SbS4)2]2-dinuclear anion.In compound 4,two SbS4 tetrahedrons are linked to two Mn(1)2+ ions to form a[Mn2(?-SbS4)2]2-unit,then the neighboring[Mn2(?-SbS4)2]2-units are connected by?2-N2H4 to form a one-dimensional[{Mn2(?-SbS4)2}(?-N2H4)2]n2n-anion chain.In compound 5,the Mn(1)2+and Mn(2)2+ ions are linked by ?-N2H4 ligand and ?-SbS3 to form one-dimensional neutral[{Mn(N2H4)}2{Mn(?-SbS3)2(?-N2H4)2}(?-N2H4)2]n chain.In compound 6 and 7,the Mn(1)2+ ion are connected with Mn(2)2+ ion via the bidentate ligands ?-N2H4 and tridentate SbS3 ligands forming a three-dimensional[Mn5(N2H4)6(Sb2S5)3]n2n-.In compound 8,Cu(1)S3 and Sb(3)S3 are interconnected by co-edge to form[CuSbS4]4-unit,the[CuSbS4]4-unit and the[Sb3S6]3-unit are interconnected to construct a two-dimensional[CuSb4S7]nn-polyanion layer that containing 16 member Cu2Sb6S8 rings.The ?1?1S1:2?1S2:3?1S3 tridentate bridging coordination mode of compound 1,?-1?1S1:2?1S1 monodentate bridging coordination mode in compound 2 and 3,and the ?-1K2S1,S2:2?S1,S3 tridentate bridging coordination mode of compound 4 are all new coordination mode of the SbS4 unit.The[SbS3]3-anion coordination mode in compound 5 is similar to[SbS4]3-in compound 4,it is also a new coordination mode for[SbS3]3-unit.Using compounds 1 and 2 as catalysts,after exposing to visible light for 2.5 hours,the CV degradation rates reached 93.3%and 81.0%for 1 and 2,respectively,about 46.0%and 36.1%of the MO dye were degraded after photoreaction for 5 hours.Compounds 1 and 2 selectively photocatalyze CV degradation under visible light irradiation.2.Under the hydrothermal conditions,TMn+ is introduced into the Sn/Se system,three TM-containing selenidostannates namely[Mn(bipy)2]2[Sn2Se6](9)and[TM(bipy)3]2[Sn3Se7]2·bipy·2H2O(TM=Co(10),Ni(11))were synthesized with bipy ligand.The compound[Me2NH2]2Sn3Se7·Me2NH(12)was synthesized in a mixed solvent of DMF and water.In compound 9,two SnSe4 units form a dimeric[Sn2Se6]4-bridging ligand by co-edge.Binuclear complex[Mn(bipy)2]2[Sn2Se6]is formed by[Sn2Se6]4-anion connecting two unsaturated[Mn(bipy)2]2+ complex cations.In compounds 10 and 11,a one-dimensional x1[Sn3Se72-]chain and a two-dimensional?2[Sn3Se72-]layer are coexisting,the x1[Sn3Se72-]is composed of SnSe4 and SnSes units,and the ?2[Sn3Se72-]contains only SnSe5 structural units.Compound 12 is composed of an ?2[Sn3Se72-]anion and a[Me2NH2]+ cation as well as a free Me2NH molecule.The type of solvent and the structure directing agent have an important influence on the structure of the compounds.After exposing to visible light for 2.5 hours,the degradation efficiencies of CV were 67.1%and 81.2%when compounds 9 and 10 were used as photocatalysts,respectively.10 showed a higher catalytic efficiency than 9.3.The structures of the compounds were determined by single crystal X-ray diffractometer.The compositions and purity of samples were characterized by IR spectroscopy and elemental analysis.Their optical properties and thennal stability were also investigated.