Design,Synthesis,Multiphoton Absorption And Electrochemical Properties Of Dinuclear Ruthenium Complexes With Tripyridine

As a nonlinear optical material,the complex has the advantages of high stability of inorganic materials and designability of organic materials,which has attracted people's attention.The octahedral polypyridine ruthenium complexes have the advantages of kinetic inertness,thermodynamic stability,rich photophysical information,and anti-tumor activity,which make the complexes have a bright application background in the field of biomedicine.In this thesis,a series of terpyridine dinuclear ruthenium complexes with nonlinear optical activity were designed and synthesized.By modifying the main ligand and auxiliary ligand,the nonlinear optical and biological properties of the dinuclear ruthenium complexes were optimized.The photophysical and electrochemical properties of the complex were systematically studied,the structure-activity relationship was clarified based on the crystal data,and the application of the complex in photodynamic therapy and nucleic acid binding was explored.1.The design,synthesis,multiphoton absorption and electrochemical properties of ferrocene-based terpyridine heteronuclear ruthenium complexesFerrocene terpyridine was selected as the main ligand,meanwhile,N^N^N-type and C^N^C-type terpyridine derivatives were selected as auxiliary ligands,then ferrocene heteronuclear ruthenium complexes FR1,FR2,FR3,FR4 were designed and synthesized.The C^N^C-type ligand,intermediate and a single crystal of N^N^N-type complex were obtained.The crystal structure data showed that the planarity of the ligand became better by coordination with Ru(?).Compared with the ligand molecule,the delocalization of the complex is enhanced,and the conjugated system becomes larger.Compared with the N^N^N-type,the coordination bond of the C^N^C-type complex is shorter,which indicates that C^N^C-type complex is more stable.The study of absorption spectrum properties shows that the maximum absorption wavelength of the C^N^C-type complex(FR4)had a certain degree of red shift than that of the N^N^N-type complex.The results of multiphoton absorption experiments showed that FR4 had the largest multiphoton absorption cross section.Combined with the theoretical calculation results,it can be known that FR4 had a greater degree of electron delocalization and stronger electron mobility.The results of cyclic voltammetry experiments showed that the redox peaks of the four complexes were negatively shifted compared with the ferrocene terpyridine ligand,which indicates that the electron cloud density on the ferrocene group is enhanced after coordination with Ru²⁺.The photodynamic activity experiment results show that the four ferrocene heteronuclear ruthenium complexes all have higher singlet oxygen yields.2.Design,synthesis,crystal structure and properties of terpyridine dinuclear ruthenium complexes containing planar auxiliary ligandsWith Ru²⁺as the central metal,the bis-terpyridine ligand was selected as the bridge,and the rigid planes ligand(o-phenanthroline,hydroxyterpyridine,and ethyl vanillin terpyridine)were used as auxiliary ligands.Three types of different water solubility and biocompatible dinuclear ruthenium complexes(R3-1,R3-2,R3-3)were designed and synthesized.A single crystal of one ligand and two complexes was obtained.The crystal structure data showed that after the complex was formed,the intramolecular conjugated system increased significantly,and the hydrogen on the terminal hydroxyl group of hydroxyterpyridine ionized in the solution to form an oxygen anion.Combined with theoretical calculations,it is found that with the expansion of the molecular conjugate system and the influence of the electron-donating effect of oxygen anions,R3-2 and R3-3 showed stronger electronic mobility.The experimental results of nonlinear optics showed that three complexes all had larger multiphoton absorption cross-sections,and the nonlinear optical properties of R3-3were the most excellent.The results of oil-water separation experiments showed that the three complexes had good solubility in water,which was beneficial to the application in organisms.R3-3 had better solubility in water than R3-1 and R3-2 due to the introduction of ether oxygen chains.DNA titration experiments found that three complexes had strong DNA binding ability and interact with DNA in a typical insertion mode;among them,the dinuclear ruthenium phenanthroline complex had a significant increase in fluorescence after binding to DNA.3.The design,synthesis,photoelectric properties and biological application of different push-pull electron-based terpyridine dinuclear ruthenium complexesOn the basis of the research in the previous chapter,the double terpyridine ligand was still used as a bridge.By modifying the auxiliary ligand single terpyridine,we designed different push-pull electron groups and adjusted the electron donating-accepting ability,then a series of photodynamically active terpyridine dinuclear ruthenium complexes was synthesized.The terpyridine dinuclear ruthenium complexes(R4-1,R4-2,R4-3,R4-4)were characterized by a series of test methods such as proton nuclear magnetic resonance spectroscopy,mass spectrometry,and infrared spectroscopy.This thesis systematically studied the effects of ligands with different push-pull electron groups on the photoelectric properties and biological activities of the terpyridine dinuclear ruthenium complex.The results of nonlinear optical experiments showed that the multiphoton absorption cross section of the electron-donating terpyridine dinuclear ruthenium complex was larger than that of the electron-withdrawing dinuclear ruthenium complex,which indicated that the introduction of an auxiliary ligand with strong electron donating ability was beneficial to enhance the electron delocalization of the complex,and with the enhancement of the electron donating ability,the nonlinear optical activity of the complexes showed an increasing trend.The results of cyclic voltammetry electrochemical experiments showed that the redox peak position and its half-wave potential value decreased with the increase of electron donating ability,which indicated that the dinuclear ruthenium complex auxiliary with electron donating auxiliary ligands was more prone to redox.PDT experiment results showed that dinuclear ruthenium complexes with moderate electron donating ability had higher singlet oxygen generation capacity.DNA binding experiment results showed that as the electron donating ability increasing,the DNA binding ability of ruthenium complexes increased,and the introduction of cations can enhance the DNA binding ability of dinuclear ruthenium complex coordinated with electron withdrawing group.The introduction of cations could enhance the DNA binding ability of dinuclear ruthenium complex coordinated with the electron withdrawing group.Cytotoxicity experiments show that the dinuclear ruthenium complex containing long alkoxy chains had both excellent biocompatibility and cytotoxicity.