Synthesis Of Amine-containing Phosphorescent Metal Complexes And Their Application In Self-healing Materials

In this thesis,four diimine compounds with different alkoxy chains,Phen-NH2-n?n=1?4?,were synthesized.The Ru???complexes of Ru-NH₂-n?n=1?4?were further synthesized with Phen-NH₂-n?n=1?4?as the ligand.After being fully characterized the molecular structures,photophysical properties,and electrochemical properties of Phen-NH₂-n?n=1?4?and Ru-NH₂-n?n=1?4?.Four phosphorescent self-healing gels were prepared by adding the Ru-NH₂-n?n=1?4?/DMF solution into polyacrylic acid?PAA?gel.The theoretical simulations on the ground-state geometries and the UV-visible absorption spectra of Ru-NH₂-n?n=1?4?were performed at the b3lyp/?lanl2dz+6-31g?level.1.In the powder state,the emission spectrum peak positions of Phen-NH2-1,Phen-NH₂-2,Phen-NH₂-3,and Phen-NH₂-4 are 456 nm,454 nm,450 nm,and 447 nm,respectively.As being dissolved in DMF?c=10^-55 mol/L?,all the emission spectrum peaks of Phen-NH₂-n?n=1?4?are at ca.445 nm.The energy levers of the highest occupied molecular orbitals(E_HOMO)and the lowest unoccupied molecular orbitals(E_LUMO)of Phen-NH₂-n?n=1?4?are in the range of-5.79?-5.82 eV and-3.78?-3.79 eV,respectively.2.In the powder state,the emission peaks of Ru-NH₂-1,Ru-NH₂-2,Ru-NH₂-3,and Ru-NH₂-4 are at 625 nm,611 nm,606 nm,and 604 nm,respectively,while those of Ru-NH₂-n?n=1?4?are at ca.605 nm in their DMF solution?c=10^-55 mol/L?.The E_HOMOOMO and E_LUMOUMO of Ru-NH₂-n?n=1?4?are in the range of-6.75?-5.90 eV and-4.52?-3.30eV,respectively.3.The tensile strength of the Ru-NH₂-n@PAA?n=1?4?gels are in the range of 80²00 KPa,and their fracture strains are in the range of 200%⁸00%.0.8%Ru-NH₂-n?n=1?4?doped PAA have the best stress-strain performances in all tested doping concentrations.After 12 h natural contact,the broken gels could be self-healed,and the self-healing effect is in the range of ca.48.9%[Ru-NH₂-3?0.8 wt%?@PAA]?81.7%[Ru-NH₂-4?0.8wt%?@PAA].4.The geometric structures and the UV-Vis absorption spectra of the synthesized Ru???complexes were theoretically simulated using density functional theory.The energies of the frontier molecular orbitals and the orbital component Ru-NH₂-n?n=1?4?are similar to each other.The HOMO?HOMO-4 are mainly consisted of the??Pho-NH₂?orbitals,whereas the LUMO?LUMO-4 are mainly consisted of?*?pht?orbitals.It was found that there were somewhat deviations in the UV-Vis absorption spectra of the theoretical simulation Ru-NH₂-n?n=1?4?compared with the actual experimental measurements.The these differences were tentatively assigned to the fact that the theoretical optimization and practical experimental measurements are carried out in gas phase and tight solid lattice,respectively,as well as the limitations of the simulation method and the basis set used in the simulation.