Preparation And Properties Of Titania-based Luminescent Hybrid Materials Of Lanthanide Complexes

The hybrid material combines the merits of both organic and inorganic components and is a kind of promising multi-function luminescence material.In addition,the structures and properties of hybrid materials can be tuned by adjusting and modifying the construction units.Luminescent hybrid materials have harvested great concern based on lanthanide complexes from researchers due to their tunable and multifunctional properties,as well as bearing the advantages of both complexes and matrix materials.This thesis aims at designing and synthesizing luminescent hybrid materials with good thermostability and excellent luminescence performance,and three kinds of novel luminescence hybrid materials were prepared with two terpyridine carboxylic acid ligands and one imidazophenanthroline carboxylic acid ligand as the organic modification ligands.The resulting materials were characterized by Infrared spectroscopy（IR）,elemental analysis,SEM,X-ray powder diffraction（PXRD）,thermogravimetric analysis（TGA）and photoluminescence spectroscopy（PL）,and some of the luminescent hybrid systems have been explored for the sensing properties.The full text is divided into the following four chapters:Chapter 1:The basic concepts and preparation methods of the luminescent hybrid materials based on lanthanide complexes are summarized,and the research progress of different types of luminescence hybrid materials based on lanthanide complexes is introduced.Chapter 2:A kind of highly luminescent titania-based europium（Ⅲ）hybrid material Eu（tta）₃cptpy-Ti O₂ was designed and synthesized by sol-gel method with4′-（4-carboxyphenyl）-2,2′:6′,2′′-terpyridine（Hcptpy）as the organic bridging ligand,and its thermostability and luminescence properties were studied.The result reveals that this hybrid material has good thermostability and reasonably long lifetime（1.02 ms）,and then its fluorescence sensing ability for organic solvents and metal cations was explored.Chapter 3:A novel luminescent hybrid material Eu（tta）₃NCP-Ti O₂ was prepared by covalently grafting the complex Eu（tta）₃（H₂O）₂ onto the titania matrix by sol-gel process with a large conjugated 2-（4-carboxyphenyl）imidazo[4,5-f][1,10]phenanthroline（4-HNCP）as the bridging ligand.The photochemical properties of this hybrid material are investigated,and it is used as a fluorescent probe for the detection of organic solvent nitrobenzene and metal Cu²⁺ion.Chapter 4:The complexes Eu（tta）₃（H₂O）₂ and Tb（tfa）₃（H₂O）₂ were grafted onto the mixed matrix of Si O₂@Ti O₂ core-shell microspheres with mesoporous Ti O₂ shell,respectively,with[2,2′:6′,2′′-terpyridine]-4,4′,4′′-tricarboxylic acid（H₃tctpy）as the organically modified ligand.Two multicomponent luminescent hybrid materials Eu（tta）₃tctpy-Si O₂@Ti O₂ and Tb（tfa）₃tctpy-Si O₂@Ti O₂ were prepared by the strong anchoring effect of the tricarboxylic acids of the ligand on the surface of Ti O₂,and the luminescent properties of the hybrid materials were studied.