Syntheses And Properties Of Two Series Of Polycarboxylate-based Metal Complexes

In this paper,by selecting lanthanide,copper,zinc,and cadmium ions as the central metals,1,3-adamantanedicarboxylic acid（1,3-H₂adc）and3,5-di（3,4-dicarboxylphenyloxy）benzoic acid（H₅L）as the main ligands,2,2’-bipyridine（2,2’-bpy）,4,4’-bipyridine（4,4’-bpy）,and 1,10-phenanthroline（phen）as the auxiliary ligands,eleven complexes have been synthesized under hydrothermal conditions,namely,[Ln₂（1,3-adc）₃（H₂O）₄]·xH₂O[Ln=Eu（1,x=1）,Tb（2,x=1）,Dy（3,x=2）,Er（4,x=1）],[Yb（1,3-adc）（1,3-Hadc）（H₂O）₃]·H₂O（5）,Cu₂（H₃L）₂（2,2’-bpy）₂·2H₂O（6）,Zn₂（HL）（2,2’-bpy）₂（7）,Cd₂（HL）（2,2’-bpy）₂·H₂O（8）,Cd₂（HL）（phen）₄·5H₂O（9）,Cu（H₃L）（phen）（10）,and Cu（H₃L）（4,4’-bpy）·H₂O（11）.They were characterized by X-ray single-crystal diffraction,elemental analysis,IR,X-ray powder diffraction,and thermogravimetric analysis.The photoluminescence and magnetism of the partial complexes were studied.Complexes 1-4 exhibit isostructural one-dimensional chain formed by1,3-adc linking alternately two mononuclear Ln（COO）₄ units and one dinuclear Ln₂（COO）₄ cluster.Complex 5 shows a one-dimensional zigzag chain constructed from 1,3-adc connecting Yb（III）,and the 1,3-Hadc anions are regularly arranged on two sides of the one-dimensional zigzag chain.In 1–5,the neighbouring one-dimensional chains are extended into the two-dimensional supramolecular layers by hydrogen-bonding interactions.Complexes 6 and 10are zero-dimensional structures.Complexes 7 and 8 possess similar three-dimensional frameworks.Complex 9 shows a one-dimensional chain structure.Complex 11 displays two-dimensional layer structure.In 6–11,the zero-dimensional or low-dimensional structures are extended into the high-dimensional supramolecular structures by hydrogen-bonding interactions.Complexes 1-3 and 5 show the characteristic luminescent properties of lanthanide ions.Complexes 7-9 exhibit the luminescent properties of organic ligands.Complex 3 displays a field-induced slow magnetic relaxation behavior.Complexes 6 and 11 indicate the antiferromagnetic interactions between the Cu（II）ions.