Synthesis Of Metalloporphyrin Derivatives And Their Application In Self-healing Materials

In this thesis,a series of porphyrin derivatives functionalized with methoxycarbonyl groups,carboxyl groups or hydrazide groups,and corresponding metal porphyrin derivatives with Zn²⁺or Cu²⁺as the center ions were synthesized.The structures of these compounds were characterized by infrared spectroscopy,and ultraviolet-visible absorption spectroscopy,and their photophysical properties were tested using a fluorescence spectrometer.The metal porphyrin derivatives were added into the polyacrylic acid gel to preprare the self-healing luminescent oranganic gels.The stress-strain tensile test and cyclic tensile test were used to analyze their self-healing characters.At last,the ground state geometries and UV-visible absorption spectra of the synthesized porphyrin derivatives were theoretically simulated at b3lyp/?lanl2dz+6-31g?level.1.The strong absorption band of the synthesized porphyrins and metalloporphyrin derivatives was found to be at ca.420 nm in their ultraviolet-visible absorption spectra.While the maximum emission of Por-COOCH₃,CuPor-COOCH₃and ZnPor-COOCH₃ locate at ca.735 nm,ca.530 nm,and ca.525 nm,respectively.Por-COOH,CuPor-COOH and ZnPor-COOH have the maximum emission peaks of about 720 nm,415 nm,and 410 nm,respectively.Por-CONHNH₂,CuPor-CONHNH₂and ZnPor-CONHNH₂ present their maximum emission peaks at ca.760 nm,ca.550nm,and ca.540 nm.2.The self-healing luminescent gel material was prepared by adding the metal porphyrin derivatives into the polyacrylic acid gel.According to the stres s-strain tests,the tensile strength of these gels is in the ragne of 20 kPa?200 kPa.The breaking strains are in the range of 50%?600%.Among all the prepared gels,the ZnPor-CONHNH₂?0.6wt%?@PAA gel has the maximum tensil e strength of ca.200 kPa and the maximum fracture of ca.530%.After 12 h ours of healing procedure,the broken ZnPor-CONHNH₂?0.6wt%?@PAA gel has a maximum fracture stress of 120 kPa with the best self-healing character of ca.59.7%.3.According to the fact that 0.6 wt%metal porphyrin containg PAA gels have the best tensile character,the photophysical properties of these organic g els were systametically investigated.As a result,Por-COOCH₃?0.6wt%?@PAA,CuPor-COOCH₃?0.6wt%?@PAA and ZnPor-COOCH₃?0.6wt%?@PAA have the m aximum emission at 656 nm?615 nm?620 nm,respectively.Por-COOH?0.6w t%?@PAA,CuPor-COOH?0.6wt%?@PAA and ZnPor-COOH?0.6wt%?@PAA show their maximum emission at ca.605 nm,ca,660 nm,ca,670 nm,respectively.And Por-CONHNH₂?0.6wt%?@PAA,CuPor-CONHNH₂?0.6wt%?@PAAand ZnPo r-CONHNH₂?0.6wt%?@PAApresent the maximum emission peaks at ca.545 nm,660 nm,and 665 nm,respectively.The emission spectral difference between the prophorine and the organic gels should be assigned to the different micro-e nviroments around the luminescent molecules.4.The ground-state geometries and UV-Vis absorptive spectra of the synthesized porphyrin derivatives were simulated at b3lyp/?lanl2dz+6-31g?level.The theoretical simulation results show that the absorption peaks of these porphyrin derivatives mainly locate at ca.420 nm,which is consistent with the experimental results.The LUMO and HOMO of ZnPor-CONHNH₂ are found to be mainly composed of??Por,380.77%?,while LUMO+2,LUMO+3,and LUMO+4 are mainly composed of?*?-CONHNH₂?.In addition,the E_HOMO and E_LUMO of ZnPor-CONHNH₂ are-5.53 eV and-2.55 eV,respectively,with the energy gap??35?E?of 2.98 eV.The S1 state absorption of ZnPor-CONHNH₂ corresponds to the mixed electronic transitions of H-1?L+1?38%?,H?L?61%?with an oscillator strength of 0.0398.All in all,the theoretically simulated absorption spectra are in good agreement with the experimentally measured ones,and the slight deviation between the theoretical optimizations and experimental measurements should be partially assigned limitations of the simulation methods and the basis sets used in the simulations.