Hydro/solvothermal Synthesis,Structures And Properties Of Lanthanide,Lanthanide-transition Metal Complexes

Lanthanide complexes and lanthanide-transistion complexes have practical applications in many fields due to their special electronic,spectroscopic and magnetic properties.Now,a variety of architectures and structures are reported,such as ball-like,cage-like,tubular-like,drum-like and multishell.With the discovery of high-nuclearity lanthanide metal clusters,some of which possessing both exquisite structural beauty and fascinating properties.Lanthanide-transistion metal clusters also have excellent properties and interesting structures.And,researchers prepare a series of high-nuclesarity lanthanide metal clusters by assembling 4f-3d clusters.At present,hydro/solvothermal as an experimental methods is used to synthesize high-nuclearity metal clusters.Under proper pH value,researchers can control the hydrolysis of lanthanide ions with special ligands.Hydro/solvothermal reaction is one of the common synthesis methods.It is worth discussing that how to compose high-nuclearity metal clusters and high-nuclearity lanthanide-transistion metal clusters under the hydro/solvothermal conditions.In this paper,three novel lanthanide metal compounds and two high-nuclearity lanthanide-transistion metal clusters were synthesized under the hydro/solvothermal conditions,including two lanthanide metal ploymers:[Er(dcd)(IN)(OH)]·H2O(1),[Er2(dcd)(IDA)2]·3H2O(2)(ded = 3,3-dimethylcyclopropane-1,2-dicarboxylate dianion,IN = isonicotinic acid,IDA = iminodiacetic acid);one lanthanide metal cluster:[Gd2(chc)5(OH)]·H2O(3)(chc = cyclohexanecarboxylic acid);and two high-nuclearity lanthanide-transistion metal clusters:[Nd20Ni21(IDA)15(GA)12(OAc)3(EtO)6(CO3)6(C2O4)3(?3-OH)21(?2-OH)15]·15H30(4),[Nd20Co24(IDA)27(C8O7N2H10)3(OAc)3(CO3)6(C2O4)3(?3-OH)21(?2-OH)3](H3O)3·21H2O(5)(GA = Glycolic acid,C8O7N2H10 = iminodiacetic acid dimer).The structures and properties of these materials were characterized by X-ray single crystal diffractometer,X-ray powder diffraction,infrared absorption spectroscopy and thermogravimetric analysis.[Er(dcd)(IN)(OH)]·H2O(1)crystallizes in the monoclinic space group P21,which synthesized by main ligand(dohd)and auxiliary ligand(HIN)under the hydrothermal conditions.3,3-Dimethylcyclopropane-1,2-dicarboxylic acid,which is one of the hydrolysate of Dohd,connects to Er(III)with iosnicotinic acid anionic.[Er2(dcd)(IDA)2]·3H2O(2)crystallizes in the monoclinic space group P21,which synthesized by main ligand(dohd)and auxiliary ligand(H2IDA)under the hydrothermal conditions.3,3-Dimethylcyclopropane-1,2-dicarboxylic acid,which is one of the hydrolysate of Dohd,connects to Er(?)with iminodiacetic acid anionic.[Gd2(chc)5(OH)]·H2O(3)crystallizes in the monoclinic space group P21,which synthesized by main ligand(chc)and anionic template(NaCl)under the hydrothermal conditions.Lanthanide ions Gd(?)connect to each other by ?3-OH and oxygen atoms in cyclohexanecarboxylic acid,which forms a one-dimensional chain structure.[Nd20Ni21(IDA)15(GA)12(OAC)3(EtO)6(CO3)6(C2O4)3(?3-OH)21(?2-OH)·15]·15H3O(4)crystallizes in the trigonal space group P3cl,which synthesized by transistion metal(Nickel(?)acetate tetrahydrate)and H2IDA ligand under the hydro/solvothermal conditions,Nd20Ni21 is zero-dimension cluster,and carbonate ions,acetate ions,oxalate ions and hydroxylacetic ions come from the decomposition of ligand.[Nd20Co24(IDA)27(C8O7N2H10)3(OAC)3(CO3)6(C2O4)3(?3-OH)21(?2-OH)3]·(H3O)3·21H2O(5)crystallizes in the hexagonal space group P63/m,which synthesized by transistion metal(Cobalt(II)acetate tetrahydrate)and H2IDA ligand under the hydro/solvothermal conditions.The inner-core structure of compound 5 is similar to compound 4,which connect six[Co(IDA)2]2-units outside the core,and carbonate ions,acetate ions and oxalate ions come from the decomposition of ligand.