Synthesis And Properties Of Two Types Of Polycarboxylate-Based Lanthanide Complexes

In this paper,by selecting lanthanide ions as the central metals,2,4,6-tri(carboxymethylmercapto)-1,3,5-triazine acid(H3TCT)and1,3-adamantane dicarboxylic acid(H2ADC)as the main ligands,and1,10-phenanthroline as the auxiliary ligand,fourteen lanthanide organic complexes were synthesized under conventional and hydrothermal conditions,namely,[Ln2(TCT)2(H2O)6]·6H2O [Ln = Tb(1),Dy(2),Ho(3),Er(4),Tm(5),Yb(6),Lu(7)],[La(ADC)2(phen)](8),[Ln(ADC)2(phen)(H2O)]·H2O [Ln = Sm(9),Eu(10),Tb(11),Dy(12)] and [Ln(ADC)(phen)(OH)] [Ln = Er(13),Yb(14)].These complexes were characterized by elemental analysis,IR,thermal analysis,X-ray powder diffraction,and X-ray single crystal diffraction.At the same time,the luminescent and magnetic properties of the partial complexes were measured by fluorescence spectrometer and magnetometer.Complexes 1-7 possess a series of discrete binuclear structures.The adjacent binuclear molecules are extended into a three-dimensional(3D)supramolecular structure by hydrogen bonding and π-π interaction.Complex 8possesses a one-dimensional(1D)chain structure,and complexes 9-12 possess a series of discrete dinuclear structures.In 8-12,adjacent structural units are extended into high-dimensional supramolecular structure by π-π stacking interaction and hydrogen bonding.Complexes 13 and 14 possess two-dimensional(2D)layer structures constructed from the binuclear Ln2(ADC)4 units.Complexes 1 and 2 show the characteristic fluorescent emissions of TbIII and DyIII,respectively,and complex 6 displays a near-infrared emission of YbIII.Complexes 9-14 all show the characteristic emissions of lanthanide ions.Complexes 2 and 12 exhibit a field-induced slow magnetic relaxation behavior.