Study On The Construction And Properties Of 3d-4f Isometallic Complexes Based On Amine Phenol Ligands

Rare earth elements have unique optical,electrical,magnetic and other physical and chemical properties,which have potential application value in multifunctional materials.Researchers have often used rare earth complexes as a single functional material,and few researchers have used magnetic properties and fluorescence properties of rare earth ions in the synthesis magnetic-luminescent bifunctional molecular materials.In view of the magnetic luminescent bifunctional molecule material is still relatively less,so this paper uses tris(2-aminoethyl)amine as the skeleton into 2-hydroxy-3-methoxybenzaldehyde,3-formylsalicylic acid and two amine-phenol ligands were obtained by reducing,built nine3d-4f heterometallic polynuclear complexs with the ligand segmentation method.The structure,spectral properties and magnetic properties of 3d-4f heterometallic polynuclear complexes were studied by single crystal diffractometer,elemental analysis,IR spectroscopy,fluorescence spectroscopy,X-ray powder diffractometer,TG and magnetic measurement system has been investigated in detail.In chapter 1,summarizes the background of this research and the status quo,a brief summary and review of the research progress of 3d-4f heterometallic single molecular magnets,research progress of dual functional molecule material magnetic light.Combined with the domestic situation foreign research,the paper clarifies the research progress on the topic basis and achieved.In chapter 2,mainly studied the tris(((2-hydroxy-3-methoxybenzy1)amino)ethyl)amine1as ligand by double solvent(methanol: chloroform = 1:1)isothermal evaporation method obtained six 3d-4f heterometallic trinuclear complexes of [M2LnL2]·2ClO4·H2O(M = Ni,Ln= Gd(1),Tb(2),Dy(3);M = Zn,Ln = Gd(4),Tb(5),Dy(6)),And the crystal structure,spectra and magnetic properties were characterized in detail.The single-crystal X-ray diffraction analysis indicated that complexes 1-6 have same crystal structure,monoclinic crystal system,P21/c space group.Magnetic properties investigations showed that complexes1-3 exhibited ferromagnetic coupling between the Ni(II)and Ln(III)ions.complex 3exhibited a very weak field-induced slow relaxation of magnetization,and has a plurality of magnetic relaxation process.The complexes 5 and 6 exhibit a typical field-induced slow relaxation of magnetization and the butterfly hysteresis loop is observed in the fielddependent magnetization curve at complex 6.entropy changes of complex 1 reach 9.31 J kg-1K-1 at 2 K and 50 kOe.Fluorescence spectrum analysis showed that the organic ligand L3-could be used as the ligand to sensitize the rare earth ions,complexes 3,5 and 6 are narrow-band characteristic of rare earth ion emission peak.In chapter 3,mainly through the ligand segmentation method obtained three 3d-4f heterometallic six nuclear complexes [Ni4Ln2(L1)4(NO3)2]·4NO3(Ln = Gd(7),Tb(8),Dy(9))based on amine-phenol ligands,and its crystal structure,thermal stability,magnetism and so on has carried on the detailed characterization.Single crystal test results show that the crystal of complex 7 crystallized in the triclinic crystal system,P-1 space group,complexes 8and 9 crystallizes in the trigonal crystal system,R-3 space group.Magnetic properties investigations showed that complexes 7-9 exhibited weak ferromagnetic coupling between the Ni(II)and Ln(III)ions and complex 9 exhibited a very weak field-induced slow relaxation of magnetization.