Synthesis,Structure Characterization And Property Studies Of New Hydrazone And Their Rare Earth Complexes

As a special class of schiff base compound. Hydrazone has unique multi-gear coordination structure and strong coordination ability, which makes it a great potention in organic synthesis interm ediates, functional materials an so on. Special electronic arrangement of rare earth elements makes it has a unique nature in the light, electricity, magnetism and so on, which attracts domestic and foreign scientists to study their synthesis, properties. Once binded, the original features of rare-earth ions and ligands will be modificated largely. The study of hydrazone rare earth complexes about their synthesis, structure and nature, will provide abroad scientific prospect for the functional materials’ design and development.In this paper, based on the domestic and aboard reaserch situation of hydrazone and their rare earth complexes, we studied the hydrothermal synthesis and rare earth complexes’s thermo dynamic property with the core of orthogonal test optimization.Throngh long-term theoretical research and related experiments, this thesis mainly conducted the following works:(1) Designed and synthesized three new single hydrazone compounds first time: p-methoxy acetophenone benzoylhydrazone, p-methoxy acetophenone4-chloro benzoylhydrazone and benzylidene phenyl ethyl ketone benzoyl hydrazone. By the means of orthogonal test, focused on the esterification and hydrazine reaction, we got the optimum conditions. When the solvent volume was50ml, catalyst was10ml, reaction time was8h, the easterification had the highest yield. When the solvent volume was35ml, reactant ratio was1:4, hydrazine reaction got the highest yield.(2) By elemental analysis, UV, infrared spectroscopy to characterize their composition. Tofurther define the structures of the hydrazone compounds, by the traditional method of solvent evaporation, first time we got the single crystal of p-methoxy acetophenone4-chloro benzoylhydrazone, and we analyzed its crystal structure, We also analyzed another new type hydrazone benzylidene phenyl ethyl ketone benzoyl hydrazone, the crystal belongs to triclinic system, space group is P-l.(3) By the methods of hydrothermal synthesis, five rare earth nitrates with the p-methoxy acetophenone benzoylhydrazone and the p-methoxy acetophenone4-chloro benzoylhydrazone were designed and synthesized. We defined the composition of the series of binary complexes by elemental analysis, UV, IR, X-ray power diffration and other physico-chemical tools, suggesting that their structures were [Re(C16H15N2O2)2]·2H2O,[Re(C16H15N2O2C)2]·2H2O(Re=La, Ce, Sm, Nd, Eu). Each rare earth ions had similar atomic orbitals and coordination environment, according to the above characterizations, we suggested the complex structures.(4) According to the analysis of fluorescence spectra, the fluorescence intensitys of La, Ce, Nd complexes were stronger than the ligands, which could be used as potential active material s.(5) Based on the synthesis, structure characterization, we discussed the thermodynamic properties of the two series of hydrazone and their rare earth complexes. Firstly, we tested the low-temperature moore heat capacity of two series of hydrazone and its La complex, using the least square method, the experimental data was polynomial fitted, caculated the smoothed heat capacity values, enthalpy change relative to298.15K, entropy, Gibbs free energy change of hydrazone and its La complexes at a certain temperature. Simultaneously, we not only tested the solution enthalpy of rare earth complexes in DMF, but also studied the relationship between the rare earth elements atomic number and their solution enthalpy. Finally, we dicussed the stability of the complexes by TG-DSC thermal decomposition.