Synthesis,Multiphoton Absorption And Biological Imaging Of Tripyridine Derivatives And Iron/Manganese Complexes

In recent years,functional complexes have unique advantages in the field of nonlinear optics,such as good solubility,high light stability,modifiable and good bio-compatibility.The structures can accurately determine through modern analysis and testing methods.So,it has attracted the attention of scientists.However,the complexes with multi-photon absorption properties and biological applications are rarely reported.Based on the bioimaging application of multiphoton absorption complexes,a series of organic ligands were designed and synthesized in this dissertation.The biocompatibility of the ligands and multi-photon absorption properties were enhanced by introducingtetrastyrene,Dibutylaminophenyl and sulfonate.Combined with the structural characteristics of low toxicity transition metal ions with various spintronic configurations,the bioactive multi-photon absorption transition metal（Fe,Mn）complexes were prepared at low cost.It is of great scientific significance and potential application value to systematically study the photophysical properties and the multi-photon absorption effect of the complexes.The main contents of this dissertation are as follows:1.A three-photon probe for highly selective and sensitive detection of Ag⁺bearing an AIE fluorophoreThe tetrastyrene tridipyridine derivative Tpy-Hex with good lipid solubility was synthesized by using tetrastyrene tridipyridine（Tpy）as the main part.The hexyl chain was introduced to improve the solubility of the compound.Tpy-Hex can quantitatively detect Ag⁺in cells and the environment at the micromol level.The three-photon absorption cross section of Tpy-Hex increased 10 times at 1550 nm（NIR II）excitation when Tpy-Hex combined with Ag⁺.Fluorescence biologic imaging results showed that Tpy-Hex couled visualized exogenous Ag⁺in He La cells and in vivo imaging of Ag⁺poisoned mice.2.Design,synthesis,multiphoton absorption and photodynamic/chemical kinetic activity of tetrastyrene terpyridine Fe（II/III）and Mn（II）complexesA series of multi-photon absorption transition metal（Fe,Mn）complexes（FA-Fe Cl₃,FA-Fe-FA,FA-Fe-L,FA-Mn Cl₂,FA-Mn-FA）were designed and synthesized with the larger conjugated tetrastyrene tridipyridine as the ligand.The photophysical properties of five complexes were studied systematically.The mechanism of charge transition in UV-vis absorption spectra were explained in detail by the experiment and theoretical calculation.The results showed that FA-Mn Cl₂and FA-Mn-FA have good AIE properties and a good singlet oxygen（¹O₂）yield,which could effectively kill cancer cells and obtain photodynamic therapy effect.FA-Fe-FA and FA-Fe-L can react with H₂O₂to produce hydroxyl radical（·OH）because of the divalent iron.It can promote the apoptosis of cancer cells rapidly and achieve the effect of chemodynamic therapy.3.Design,synthesis,crystal structures,multiphoton absorption and biological application of Dibutylaminophenyl terpyridine Fe（II/III）and Mn（II）complexesThe multiphoton absorption transition metal Fe（II/III）and Mn（II/III）complexes（FD-Fe Cl₃,FD-Fe-FD,FD-Fe-L,FD-Mn Cl₂,FD-Mn-FD）were designed and synthesized using Dibutylaminophenyl tribipyridine as the main ligands.The detailed energy levels of the corresponding transition orbits were obtained by UV-vis absorption spectra and theoretical calculations（TD-DFT）.The results of nonlinear optical properties showed that the complexes FD-Fe Cl₃,FD-Fe-FD and FD-Fe-L have large three-photon absorption cross-sections in the second region of the near infrared,and the absorption cross-sections are higher than 100(10^-80cm⁶s²photon^-2).The complexes FD-Mn Cl₂and FD-Mn-FD have good AIE activity in methanol/water.Biological imaging showed that FD-Mn-FD could target lipid droplets and FD-Mn Cl₂could target mitochondria.Therefore,FD-Mn Cl₂and FD-Mn-FD could be used as fluorescent probes to monitor the dynamic changes of intracellular lipid droplets and mitochondria.4.Design,synthesis,crystal structures,multiphoton absorption and specific recognition of triphenylamine sulfonate terpyridine Fe（II/III）and Mn（II）complexesA series of multiphoton absorption transition metal Fe and Mn complexes（FS-Fe Cl₃,FS-Fe-FS,FS-Fe-L,FS-Mn Cl₂,FS-Mn-FS）were designed and synthesized with triphenylamine sulfonate tridipyridine as the main ligand.The introduction of sulfonate groups increases the solubility of the complexes.The mechanism of charge transition and the difference of photophysical properties between the complexes and the auxiliary ligands were studied in detail by experiments and theoretical calculations.The results of nonlinear optical properties showed that FS-Fe Cl₃,FS-Fe-FS and FS-Fe-L had excellent two-photon absorption cross-sections and three-photon absorption cross-sections.FS-Mn Cl₂and FS-Mn-FS were found to be highly sensitive to bovine serum protein（BSA）.The reaction mechanism was explained by viscosity test.The nonlinear optical test showed that the manganese complexes（FS-Mn Cl₂and FS-Mn-FS）have excellent multi-photon absorption activity when interact with BSA.