Design,Synthesis,Multi-photon Absorption And Cell Imaging Of Halogenated Carbazole Terpyridine Complexes

To date,optical functional complex materials play an important role in the fields of information,energy and life sciences due to their designable structures,high stability,adjustable light-emitting wavelength and excellent photophysical properties.Carbazole,a typical long-life blue light emitting material,can be further modified to obtain a series of organic ligands with the characteristics of good planarity,high electron delocalization and long emission life.In this dissertation,a series of optical functional complexes were designed and synthesized with Zn,Eu,Gd,Yb and halogenated carbazole terpyridine as ligands.The photophysical properties were studied systematically,and explored their potential application in cell imaging.1.Design,synthesis,photophysical properties and cell imaging of-Br/-I modified carbazolyl terpyridine Zn(?)complexesA series of zinc(?)complexes(ZnKt1?3-PF6-,ZnKt1?3-NO3-)with high biological activity were designed and synthesized with halogenated carbazole terpyridine as ligand.The complexes with NO3-as anion show better solubility than PF6-and the mechanism of electron transition was elucidated with DFT theoretical calculations and UV-vis absorption spectra.The optical results showed that ZnKt1?3-PF6-,ZnKt1?3-NO3-had good single-photon fluorescence emission,delayed fluorescence emission and aggregation-induced luminescence effects.Notably,the delayed fluorescence properties of the complexes were optimized after introducing halogen atoms.Furthermore,the investigations on nonlinear optical properties indicated that the complexes exhibit excellent two/three-photon absorption activity at 780 nm and 1300 nm.Moreover,cell co-localization and fluorescence lifetime imaging showed that ZnKt1?3-NO3-had specific lysosomes targeting,and show time-resolved fluorescence lifetime images of lysosomes.2.Design,synthesis and photophysical properties of lysosomal targeting?-diketone/carbazolyl terpyridine Eu(?)complexesThree europium complexes(Eu-Kti?3)with high fluorescence quantum yield and good monochromaticity were designed and synthesized by halogenated carbazole terpyridine and thiophene ?-diketone as ligands.The target complexes have been comprehensive characterized by modern analytical testing techniques.After introduction of halogen atoms,the changes of linear and nonlinear optical properties were analyzed.The results of linear optical properties revealed that the complexes possessed large Stokes shift and characteristic emission band of europium appeared at 590?620 nm.And the energy transfer efficiency between the tripyridine ligand and Eu(?)in the complex increased gradually with the decrease of temperature.In addition,under the excitation of wavelength in the near-infrared region(?740 nm,?1200 nm),Eu-Kt1?3 had large two/three-photon effective absorption cross-sections.Additionally,the MTT test and co-localization experiments showed that three europium complexes exhibited low-toxic could specifically target lysosomes,the Pearson's coefficient as high as 0.91.3.Design,synthesis and multiphoton properties of Gd(?)complexes with photodynamic activityMotivated by the above investigations of complexes Eu-Kt1?3,a series of gadolinium complexes(Gd-Kt1?3)with photodynamic activity were synthesized by thiophene ?-diketone and halogenated carbazole terpyridine as ligands.The investigations on nonlinear optical properties showed that the complexes possessed large effective multi-photon absorption cross-section in the near infrared region.The halogen atom optimized the multi-photon absorption properties of the complexes.In order to study the effect of photodynamic therapy,DCFH-DA and ABDA were used to detect the production of singlet oxygen,the results showed that Gd-Kt2?3 could produce singlet oxygen effectively.Also the ESR spectroscopy verifiy the existence of singlet oxygen.Confocal imaging and MTT test revealed that under light irradiation,the complex Gd-Kt3 had significant phototoxic effect to tumor cells,caused cell apoptosis rapidly,showing excellent Photodynamic therapy(PDT)effects.4.Design,synthesis and multiphoton absorption of thiophene ?-diketone/carbazolyl terpyridine Yb(?)complexesBased on the above work,three ytterbium complexes(Yb-Kt1?3)were synthesized by using Kt1?3 and HTTA as the ligands.The nonlinear optical absorption properties results indicated that Yb-Kt1?3 possessed good multi-photon absorption properties.In addition,the closed-aperture Z scan measurements found that the complexes had larger third-order nonlinear optical susceptibility ?(3).Notably,after introducing of halogen atoms,the complexes behave better electronic exchanges and performed better nonlinear optical absorption activity.