Synthesis Of Novel Ligands Containing Hydroxyl Groups And Its Applications In Luminescent Lanthanide Hybrid Materials

Trivalent lanthanide complexes with photoluminescence properties has been attached importance by the outstanding chemists, because its some good features, such as the strong emission spectra and high chromatographic purity, the wide emission band covering the ultraviolet visible near infrared region, and its a wide range of lifetimes is from the seconds level to the microseconds level. At present, these properties have attracted much attention in the diagnostic tools, the sensors, the optical fiber, the exciter and the amplifier, has been applied to various fields and electroluminescence material etc.. It is a pity, the actual applications of rare earth coordination compounds are only limited to a certain extent, because of their poor thermal stability and low mechanical strength. Aiming at the above problems, a feasible solution is to introduce a stable complex rigid matrix, such as silica or titania based materials. The incorporation of these matrices in luminescent rare earth complexes, namely “inorganic-organic” hybrid materials, which not only improve the imaging and thermal stability of the rare earth complexes, but also avoid self quenching concentration effect.In the hybrid material structure, connecting complexes and Si O2 matrix by chemical bonds, therefore, in the preparation process, a large number of siloxane coupling agent is used. However, because the siloxane is sensitive to water, even if the humidity in the air condition can also make it hydrolyzes, so that makes the intermediate purification very difficult, and further affects the purity of the final product.To this end, we start from the basic principle of coordination chemistry, combining with the preparation of the “inorganic-organic” hybrid materials with the sol-gel technique, proposing that the idea of synthesis of composite luminescent materials with ligands containing hydroxyl institute of siloxane coupling agents. First of all, selecting organic heterocyclic molecules of the better coordination ability and the introduction of hydroxyl groups in its structure by means of organic synthesis. After preparing complexes by synthesis of ligands and transition metal ions, directly to hydrolytic polycondensation of the hydroxyl and ethyl orthosilicate occurs, thus avoiding the use of silicone coupling agent, making the intermediate purification relatively easy, so as to ensure the purity of the final material. The following is a series of the research results achieved:1, Use amino acid as the bridging agent building complexes of rare earth mesoporous luminescent material and start from the basic principle of rare earth coordination chemistry, combining with the sol-gel chemistry and organic molecule modification technology and method and using amino acid as cross-linking agent to build the rare earth mesoporous luminescent materials. The particular organic ligand molecules with excellent photosensitive chemical properties have been modified in the structure, and further reacted with amino acids to the novel organic ligand. In the formed rare earth complexes, and then through the functional groups in amino acid molecules which the rare earth ion did not participate in the coordination with, and have further hydrolysis polycondensation with the mesoporous matrix precursor, to finally obtain the rare earth mesoporous luminescent materials.2, Taking β-diketone compounds as the initial ligand, through reacting with alcohols with long chain to introduce hydroxyl, to get the new organic ligand containing hydroxyl. Finally, through the reaction of hydroxyl and inorganic matrix by dehydration condensation build hybrid materials, to obtain rare earth luminescent hybrid materials3, Through the modification of the Pyridine-2,6-carboxylic acid, by the acyl chloride, and reacting with short chain alcohol amine molecule, introducing hydroxyl, then reacting with mesoporous materials by dehydration condensation.4, Through the modification of the Phthalic acid, by the acyl chloride, and reacting with short chain alcohol amine molecule, introducing hydroxyl, then reacting with mesoporous materials by dehydration condensation.