The Synthesis And Photo Dynamic Studies On Nitrosyl Ruthenium Complex [RuCl?2mqn?₂NO]

Ruthenium complexes have attracted so much attention because of their photochemistry and photophysical properties,abundant ground state and excited state reactivity,stable thermodynamic properties,which provide a broad potential applications.Photo-induced isomerization reaction is vital for ruthenium complexes.Photoisomerizationis the basis for the design of molecular switch and molecular motor,also can be used for new type of storage medium,which is significance for the development of light catalyst,nanometer molecular devices.In the meantime,the study on the mechanism of photo dissociation of ruthenium complexes is importantfor photodynamic therapy.There are photo induced dissociation during the process of isomerization reaction for nitrosylruthenium complexes,therefore it is necessary to investigate the relationship of dissociation and isomerization and further to elucidate the mechanism of the photo reaction,in order to make a basis for further applications.In this paper,we use of density functional theory?DFT?to calculate the structures and absorption spectrums,such asIR ? NMR and UV of three nitrosylruthenium isomeric complexes,and which are agree with experimental results.Analyzing the absorption spectra and the molecular vibrational modes and studying dynamic process of the isomers of nitrosylruthenium complexes in different wavelengths,different solvents and different substituent groupsunder the excitation of light by NMR spectrum and IR spectrum technology,to obtain the basic experimental methods to control the light reaction process of nitrosylruthenium complexes.Two-dimensional correlation spectroscopy?2D COS?technology was used to study the reaction order of nitrosylruthenium complexes upon photo irradiation.The prime content of this paper include:First,intreducing the nature and history of photo reactions of ruthenium complexes,and research progress of photo-induced isomerization anddecompsition reaction of nitrosylruthenium complexes was summarized.Second,synthesizing and separating the cis-1[Ru Cl?2mqn?₂NO],cis-2[RuCl?2mqn?₂NO],trans[RuCl?2mqn?₂NO] with-Cl and2-methyl-8-hydroxyqulinolin?2mqn?as the ligands.Structures and absorption spectrumsthatinclude UV,IR and NMR spectra of three[RuCl?2mqn?₂NO]isomers were calculatedwith 6-311++G?d,p?and Lanl2 dz or Aug-cc-p VDZ-PP,which are as the basis sets.The results show that the optimized molecular configuration is reasonable,the electronic absorption peak position,vibration frequency,the H atoms spin coupling of the chemical shift values can be assignedand agree with the actually measured value.The molecular orbitals of the complexes were calculated and the electron transition were analyzed.The DFT calculation provided an important theoretical guidance for exploring reaction mechanism of nitrosylruthenium complexes.Third,the photo-induced isomerization of cis-1and trans[RuCl?2mqn?₂NO] were detected by 1H NMR spectroscopy technique.According to the absorption spectrum of isomers,we chose 420 nm and full light as the excitation wavelength,and under different excitation wavelength,we calculated out the rate constant and equilibrium constantof photo-induced isomerization reaction in CDCl3 solvent and DMSO-d6 solvent.Rate constant of full light condition is bigger than that of 420 nm.Upon photo iriadation,there are both photo isomerization and dissociation reaction observedin CDCl3 solvent,but only dissociation reaction in DMSO-d6 solvent.It provided the experimental basis for further controlling photo isomerization process.Fourth,under the full light and 420 nm ligh,the photo dynamic properties of cis-1 and trans [RuCl?2mqn?₂NO] complexes was studied by IR.And the reaction order of [RuCl?2mqn?₂NO] isomers upon photo irradiation with different wavelength and in different solvent were studied by two-dimensional correlation spectroscopy?2D COS?,which showed the reaction order of different substituents of nitrosylruthenium complexes were:dissociation first and then isomerization.The reaction order of[Ru?OAc??2mqn?₂NO] isomers are not same for different solvent.