The Synthesis And Characterization Of MOF Materials Based On Nitrogen-rich Tetraphenylethene

Tetraphenylethene?TPE?,as one of the classic aggregation-induced emission?AIE?chromophores,has become a universal component of synthetic luminescent metal-organic framework?LMOF?.Tetrakis?4-ethynylphenyl?ethylene is a member of the TPE family.Because it contains multiple extendable alkynyl groups,many different types of multidentate organic ligands can be designed through a variety of classical reactions.The metal organic framework materials based the ligand has important applications such as adsorption and sensing materials.In this dissertation,two ligands were successfully obtained through Click reaction and Sonogashira reaction.Multiple TPE-based MOFs were constructed using reticulated chemistry and their properties were explored.They are mainly divided into the following three parts:1)Based on Click chemistry,a new type of organic ligand containing multiple nitrogen-rich groups with aggregation-induced emission characteristics was prepared by coupling tetra?4-ethynylphenyl?ethylene with methyl 4-azidobenzoate,tetrakis[4-?4-carboxyphenyl??1H-1,2,3-triazol-4,1-diyl?phenyl]ethene?H₄TCPTAPE?,with a fluorescence quantum yield of 17%and a fluorescence lifetime of 2.6 ns.A complex with high porosity and stable structure[Zn₃?TCPTAPE??H₂O?₄]?1?was synthesized by solvothermal method.The structure of the complex was explored by IR analysis,thermal stability test,fluorescence property detection and X-ray single crystal diffraction,etc.in detail.Studies have shown that complex 1 has a high fluorescence quantum yield of 54%.Exploring the sensing performance of carcinogens in traditional Chinese medicines for complex 1,it showed highly sensitive and selective recognition of type I aristolochic acid?AA-I?,with a quenching efficiency of 96%,and DFT calculation the results show that photoinduced energy transfer is the main quenching mechanism.Later experimental results show that the minimum detection limit of activated complex 1 for AA-I is 1.02?M,which proves that it is a promising carcinogen luminescence sensor.2)Based on the above method,the same ligand H₄TCPTAPE was synthesized,and a complex with multiple coordination modes[Eu₂Cl?TCPTAPE?_1.5?H₂O?₂]?2?was synthesized by solvothermal method.The structure of the complex was characterized by IR analysis,thermal stability test,fluorescent properties detection and X-ray single crystal diffraction.Studies have shown that complex 2 has a fluorescence quantum yield of 24%.Exploring the sensing performance of antibiotics in water for complex 2,which shows excellent sensing performance for nitrofurazone and nitrofurantoin,with high sensitivity,selectivity,and quenching efficiency of 96%and 94%,respectively.DFT calculation results show that photoinduced energy transfer is the main quenching mechanism.The later experimental results shows that the lowest detection limit of the activated complex 2 for nitrofurazone is 0.3935?M and for nitrofurantoin 0.8056?M,which proves that it is a promising antibiotic fluorescent sensor.3)Based on Click chemistry,a nitrogen-rich octacarboxylic acid ligand with AIE character was prepared by coupling tetra?4-ethynylphenyl?ethylene with4-azidomethyl isophthalate,5,5',5",5'''-??ethylene-1,1,2,2-tetra?benzene-4,1-diyl??tetra?1H-1,2,3-triazole-4,1-Diyl??tetraisophthalic acid?H₈TCPTAPE?,with a fluorescence quantum yield of 14%and a fluorescence lifetime of 3.1 ns.Three complexes with large pores and large specific surface area H₈TCPTAPE-Cu?3?,H₈TCPTAPE-Zn?4?and H8TCPTAPE-In?5?were synthesized by solvothermal method.The structure was characterized by IR analysis,powder XRD,and thermal stability analysis.The complexes?4?and?5?show strong fluorescence emission intensity,which has potential applications for sensory recognition of macromolecules.