Study On Syntheses, Crystal Structures And Properties Of Lanthanide Complexes With Tetraiminodiphenol Macrocyclic Ligands

Ten lanthanide complexes with tetraiminodiphenol macrocyclic ligands were synthesized and characterized by physical methods in detail. The main work of this dissertation was as follows:1.Six mononuclear lanthanide complexes were synthesized by template condensation of 2,6-diformyl-4-methyphenol or 2,6-diformyl-4-chlorophenol with corresponding diamine in the presence of lanthanide ions.Several methods,including electrospray mass spectrometry（ES-MS）,X-Ray structural analysis and fluorescent spectrometry were used to characterize these complexes in detail.In room temperature,excitation of the propyldiamine-based Eu（Ⅲ） complex in methanol solution gave rise to the characteristic emissions of the Eu³⁺ ion,but the 5-azapentadiamine-based Eu（Ⅲ） complex did not presented luminescence due to its instability in solution,which was conformed by ES-MS.2.A ternary Tb complex was obtained when terpyridine was introduced to the template condensation reaction,and its crystal structure was studied by X-Ray structure analysis.This complex presented characteristic luminescence of Tb³⁺ ion in methanol solution,but strong fluorescence of ligand was also observed due to the mismatch of energies between ligand and lanthanide ion.3.On the base of mononuclear complexes,three bridged binuclear lanthanide complexes were synthesized and characterized by X-Ray structural analysis.Among the three bridged complexes,two different bridging modes are existed,one is by two CH₃COO^-,and another is by two oxygen atoms which come from one side of each of the two macrocycles.