| With the development of science and technology,the study of germanium(tin)chalcogenides have been paid close attention.Among them,germanium(tin)chalcogenides modified by lanthanide complex cations are a kind of multifunctional materials with rich structures and a wide range of applications in the fields of nonlinear optics,semiconductors,magnetism,ion exchange,catalysis and so on.Because chalcogenide anions are easily oxidized under ordinary reaction conditions,it is difficult to obtain germanium(tin)chalcogenides.High temperature solid state reaction is one of the most commonly used methods for the preparation of these compounds.In this article,38 germanium(tin)chalcogenides with lanthanide complex cations were prepared by low temperature solvothermal method,and characterized by X-ray single crystal diffraction,X-ray powder diffraction,ultraviolet spectrum,infrared spectrum and so on.The photocurrent response properties of some compounds were also studied.Thiogermanate with lanthanide N-(2-hydroxyethyl)ethylenediamine complex cations:Using N-(2-hydroxyethyl)ethylenediamine as structural directing agent,a series oflanthanidethiogermanates[La2(hda)2(da)2(?-Ge S3)2](1)and{[Ln2(hda)2(da)2][Ln2(da)4](?-Ge S3)2}n·2n Cl[Ln=Pr(2),Nd(3),Sm(4),Eu(5),Gd(6),Tb(7),Dy(8)]were synthesized by solvothermal method.Compound 1 is composed of two unsaturated ligand cations[Ln(hda)(da)]2+and[?-Ge S3]2-,which are interconnected to form a neutral[La2(hda)2(da)2(Ge S3)2]cluster.Compounds 2-8 are isostructural,and consist of unsaturated cations[Ln2(hda)2(da)2]4+,[Ln2(da)4]2+and[Ge S3]2-anion,which are interconnected to give an one-dimensional polymeric cation{[Ln2(had)2(da)2][Ln2(da)4](?-Ge S3)22-}n chain.Compounds 1-8 exhibit the energy gap range of 3.47-3.99 e V,which are wide band gap semiconductors.Thiostannate with lanthanide N-(2-hydroxyethyl)ethylenediamine complex cations:Using N-(2-hydroxyethyl)ethylenediamine as structural directing agent,two series of lanthanide thiostannates[Ln2(hda)2(da)2(Sn2Se6)]n[Ln=La(9),Ce(10),Pr(11),Nd(12),Sm(13)],[Ln3(da)5(Sn2Se6)][Ln=Eu(14),Gd(15),Tb(16),Dy(17),Ho(18),Er(19),Tm(20),Y(21)],[La2(hda)2(da)2(Sn2S6)]n(22),{[Ln2(hda)2(da)2][Ln2(da)4](?-Sn S3)2}n·2n ICl[Ln=Ce(23),Pr(24),Nd(25),Sm(26),Eu(27),Gd(28)]and[Ln3(da)5(Sn2S6)][Ln=Tb(29),Dy(30),Ho(31),Er(32),Tm(33)]were synthesized by solvothermal method.Compounds 9-33 have three different structures,among which compounds 9-13 and 22 are isostructural,and consist of unsaturated cations[Ln2(hda)2(da)2]4+and[Sn2Q6]4-anion,which are interconnected to give an one-dimensional polymeric chain.Compounds 14-21 and 29-33 are isostructural,and consist of unsaturated trinuclear lanthanum cluster cation[Ln3(da)5]4+and tin selenide dimer[Sn2Se6]4-anion,which are interconnected to form a neutral[Ln3(da)5(Sn2Q6)](Q=S,Se)cluster.Compounds 23-28 are isostructural,and consist of unsaturated cations[Ln2(hda)2(da)2]4+,[Ln2(da)4]2+and[?-Sn S3]2-anion,which are interconnected to give an one-dimensional polymeric chain.Compounds 9-21 exhibit the energy gap range of 2.13-2.60 e V,and compounds 22-33 exhibit the energy gap range of 2.73-3.46 e V,which are semiconductor properties.The photocurrent response performance of compounds 9-21were tested,and the results showed that compounds 9-21 have good photocurrent response characteristics.Thiostannate with lanthanide diglycolamine complex cations:Using diglycolamine as structural directing agent,a series of lanthanide thiostannates[Ln4(dga)6Cl2(Sn2S6)]n[Ln=Sm(34),Eu(35),Tb(36),Dy(37),Er(38)]were synthesized by solvothermal method.Compounds 34-38 are isostructural,and consist of unsaturated cations[Ln4(dga)6Cl2]4+and[Sn2S6]4-anion,which are interconnected to give an one-dimensional polymeric chain.Compounds 34-38 exhibit the energy gap range of 2.50-2.82 e V,which show semiconductor properties. |
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