Studies On Synthesis And Application Of Lanthanide And Transition Metal Functional Complexes

In this thesis,six metal complexe systems with verious functions were successfully synthesized by ligand design and metal ion selection strategy.The corresponding metal functional complexes were also characterized and fully studied.This thesis covers following seven parts:1.A brief introduction to the development of supramolecular chemistry and frontier work of metal functional complex are given and the relationship between the construction and performance of metal functional complexes has been reviewed in detail;2.A series of 2D coordination polymers 2a-2i based on imidazole carboxylic acid were synthesized by solvothermal method and their structures and solid-state luminescence properties were studied in detail.Among them,Eu³⁺complexes 2a-2c and Tb³⁺complexes 2d-2f exhibit fluorescence enhancement with the increases of halogen content in the structures.Based on this phenomenon,we also found that 2c and 2f have good fluorescence response to Fe³⁺ions,acetone molecules,and nitro-explosive molecules in a aqueous solution system.They can be used as a highly efficient and rapid quantitative fluorescence sensor and applied in the detection area of PA molecules and Fe³⁺ions;3.By changing the proportions Eu³⁺and Tb³⁺,a series of yellow luminescent materials isomorphic to 2a-2i have been synthesized.It was found through fluorescence test that by changing the proportion of rare earth ions and the excitation wavelength we can adjust the luminescent properties of this series of luminescent materials.In addition,it was also found that the complex TbEu_0.15 can perform rapid and highly sensitive quantitative luminescent detection of PA in aqueous systems;4.By solvothermal method and the self-assembly behavior of imidazolium-carboxylic acid ligands and heavy rare earth ions Er³⁺,Tm³⁺and Yb³⁺?4a-4f?,a series of one-dimensional chain coordination polymers with 1D channel 4a-4f were synthesized.By testing the performance of catalyzing the reaction between CO₂ and epoxy substrate,it can be known that this series of 1-D chain CPs is a good CO₂ cycloaddition catalyst and they have good catalytic activity for the reaction under mild conditions and high temperature and pressure conditions.5.A series of polydentate ligands based on pyrimidine-bipyridine were obtained and 8 complexes based on Ru²⁺were synthesized.Through the photocatalytic hydrogen production of complex 5-H-Ru1,it was found that the complex 5-H-Ru1 has better photocatalytic properties for hydrogen production.The TON value can reach 222 and the TOF can reach 37h^-1.However,this system has many disadvantages as a photocatalytic hydrogen-producing system and we hope that further research can be conducted to improve the efficiency of the reaction in the future;6.A series of complexes 6d-Ru-Ln based on Ru and rare-earth ions were obtained.Through the catalytic oxidation performance test,6d-Ru-Ce has the highest ability to decompose oxidized water,and its TON is 976.TOF reached 2.8s^-1.These complex reveals the potential of rare earth ions in synergistic catalysis and the ability to build molecular-grade water oxidation catalysts;7.The MOFs material,MIL-101-Fe and MIL-126-Fe,were synthesized and the performance of photocatalytic water oxidation was investigated.It was found that both MIL-101-Fe and MIL-126-Fe are good photocatalytic water oxidation catalyst and its maximum oxygen production capacity is 82.26 mmol·g^-1·h^-11 and 133.28 mmol·g^-1·h^-1.This result confirms that iron-based MOFs material catalysts are a promising class of photocatalytic oxidation catalysts.