| The organic hybrid thioarsenates(thioantimonates)crystalline materials possess various structures,which are a new class of multi-functional materials that exhibit electrical,optical and semiconductor properties.Lanthanide complexes often show magnetic,fluorescent and catalytic properties,the integration of the lanthanide complexes into the thioarsenate(thioantimonate)frameworks can not only enhance the structural diversity of the lanthanide thioarsenates(thioantimonates),but also integrate the features of the lanthanide complexes into the thioarsenates(thioantimonates).This research explored the Ln/As(Sb)/S organoalcoholic amine solvent thermal reaction system and obtained a series of lanthanide thioarsenates(thioantimonates).The crystal structures were determined,and these compounds were characterized by X-ray powder diffraction,infrared spectroscopy and solid ultraviolet-visible spectroscopy.1?Tthioarsenate with diethylene glycol amine lanthanide complex cations:Using diethylene glycol amine(hgda)as the structure-directing agent,[La16(hdga)6(dga)18(?-AsVS4)10]n(1)was obained by the solvothermal method.1comprises unsaturated dinuclear Ln3+complex ions,unsaturated tetranuclear Ln3+collocation ions,and tetrahedral[As S4]3-anion.The tetrahedral[As S4]3-unit shows two separate bridging modes,namely?-?1:?1:?1:?1-As S4and?-?1:?2:?1-As S4with the molar ratio of 1:4,and two different types of Ln3+complex ions are bridged by tetrahedral[As S4]3-units to form a 1-D neutral chain.The result demonstractes that lanthanide metal ions(Ln3+)can be also coordinated to soft base ligand[As S4]3-in organic alcohol amine solution.By changing the ratio of reactants,six other diethylene glycol amine lanthanide complex ions-bridged thioarsenates:[Ln4(dga)6(?-AsVS4)2]{Ln=La(2),Eu(3),Gd(4),Tb(5),Dy(6),Ho(7)}were successfully synthesized.These compounds are composed of unsaturated tetranuclear complex cations ions[Ln4(dga)6]3+and tetrahedral[As S4]3-anions.Ln3+lanthanide complex ions are highly unsaturated,and there are several empty coordination sites that can coordinate with multiple tetrahedral[As S4]3-units.The compounds are connected by multiple Ln-S bonds to form the first rare 2-D layered lanthanide chalcogenidoarsenates compound.The band gaps of compounds 1-7 are 2.36-2.89 e V,which show good semiconductor properties.2?Thioantimonates with ethanolamine lanthanide complex cations:Using ethanolamine(hea)as the structure-directing agent,a series of ethanolamine lanthanide complex ions-modified thioantimonates:[Ln6(ea)12(hea)4](SbVS4)2{Ln=Eu(8),Gd(9),Tb(10),Dy(11),Ho(12),Er(13)}were obained by the solvothermal method.At present,it has been reported that in the lanthanide chalcogenioantimonates compounds containing tetrahedral[Sb Q4]3-(Q=S,Se)units,the Ln3+complex cations are usually mononuclear or binuclear,while in compounds 8-13,the Ln3+complex ions are bridged by hydroxyl oxygen to form a rare hexanuclear complex[Ln6(ea)12(hea)4]6+,which further synthesizes the[Ln6(ea)12(hea)4](SbVS4)2cluster with[Sb S4]3-anion bond.The band gaps of compounds 8-13 are in the range of 2.19-3.02 e V,which show semiconductor properties and are the potential semiconductor materials.3?Thioantimonates with N-(2-hydroxyethyl)ethylenediamine lanthanide complex cations:Using N-(2-hydroxyethyl)ethylenediamine(hda)as the structure-directing agent,a series of N-(2-hydroxyethyl)ethylenediamine lanthanide complex ions-bridged thioantimonates:[Ln4(da)6(hda)2Cl2]Cl4{Ln=Sm(14),Eu(15)}and[Ln6(da)10-(?-OH)2]Cl6·2H2O{Ln=Y(16),Gd(17),Dy(18),Tb(19),Ho(20),Er(21),Tm(22)}were obained by the solvothermal method.Compounds 14-15 and 16-22 are tetranuclear and hexanuclear lanthanide clusters respectively,and the inorganic framework antimony sulfur anion does not appear in the product,therefore,four lanthanide thioantimonates[Ln4(da)8]n[Sb8S18]n{Ln=Ce(23),Pr(24),Nd(25),Sm(26)}are obtained by changing the conditions.These compounds are composed of anionic and cationic chains,forming a rare double strand structure.The chain structure of lanthanide chalcogenioantimonates compound is enriched.Under similar solvothermal conditions,two 1-D chain lanthanide chalcogenioantimonates thioantimonates[Ln6(da)8(en)2Cl2(?-Sb2IIIS5)2]{Ln=Sm(27),Eu(28)}were synthesized by adding ethylenediamine.This compounds contain[Ln4(da)6Cl2]4-and[Ln2(da)2(en)2]4-complex ions and saddle-shaped[Sb2S5]4-anion,which not only realizes the diversification of Ln3+complex cations in the same compound,but also enriches the structure of thioantimonates.4?Thioantimonates with diethylene glycol amine lanthanide complex cations:Using diethylene glycol amine(hgda)as the structure-directing agent,a series of diethylene glycol amine lanthanide complex cations-bridged thioantimonates:[Eu4(dga)6(?-SbVS4)2](29)and[Ln4(dga)6(?-Sb4IIIS9)]{Ln=Eu(30),Gd(31),Tb(32),Dy(33),Ho(34)}were obained by the solvothermal method.Under the condition of solvothermal,lanthanide chalcogenioantimonates compounds with large ion radius usually show low dimensional structure(0?1D).Compound 29 has a rare 2-D layered structure;Compounds 30-34 are the first example of lanthanide thioantimonates in 3-D network,the three-dimensional network structure of compounds 30-34 are formed by the connection of unsaturated tetranuclear[Ln4(dga)6]6+and[Sb4S9]6-anion.Under similar solvothermal conditions,another series of diethylene glycol amine lanthanide complex ions-bridged thioantimonates:[Gd4(dga)6(en)2(?-SbVS4)2](35),[Ln6(dga)8(en)2Cl2-(?-Sb2IIIS5)2]n{Ln=Tb(36),Dy(37),Ho(38)}and[Er4(dga)6Cl2(?-SbIIIS3)2](39)were synthesized by adding ethylenediamine.Compounds 36-38 are 1-D chain compound,which were bridged by unsaturated cation[Ln4(dga)6Cl2]4-,[Ln2(dga)2(en)2]4-and[Sb2S5]4-anions;Compounds 35 and 39 show a tetranuclear cluster structure. |
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