The Synthesis And Application Of Tetraphenylethylene Derivatives

Since the aggregation induced emission(AIE)phenomenon was first reported in 2001,it has rapidly become hot research topics of molecular science.Researchers have designed and synthesized many different types of AIE molecules,and they were widely applied to biochemical sensing,photodynamic therapy,photoelectric devices and biological imaging because of their excellent optical properties.As a class of the most typical molecules with AIE character,tetraphenylethylene(TPE)has caused great concern among researchers because of its easy modification and efficient optical properties.Designing and developing new AIE molecules based on TPE and expanding their applications are important development directions of AIE research.In this thesis,since TPE compounds have the characteristics of easy modification and adjustable properties,a series of new TPE derivatives were designed by introducing functional groups with TPE as the parent molecules,and their applications in adsorption,optoelectronic devices,antibacterial,mechanochromism and detection were explored.The main research contents were listed as follows:(1)Using 4-(4-aldehyde phenyl)ethylene and 4-(4-aminophenyl)porphyrin as organic structural units,hollow capsules TPE-TAP-COF was prepared by Schiff base condensation reaction.The experimental results revealed that the formation of this TPE-TAP-COF was an Ostwald ripening self-assembly process.TPE-TAP-COF was applied in the study of hemoglobin adsorption,and the adsorption amount reached 550.82 mg·g-1 after 8 hours.(2)A tetragonal metallacage was prepared by coordinating TPE derivative(TBI-TPE)with silver ion,which displayed excellent and stable fluorescent properties in solution and aggregated state.The fluorescence lifetime and quantum yield were significantly improved compared with TBI-TPE ligand.The Ag-TBI-TPE cage has a significant solvatochromic property in organic solvent.Moreover,a reversible cyclic turn-on/off mechanocharomic behavior of them was observed in the solid state.It was used for the preparation of a white lightemitting diode.(3)Ag-TBI-TPE cage was positively charged and also possessed the function of photosensitizer that produced ROS under light.Thus,Ag-TBI-TPE cage has significant antibacterial activity.After light induction,the synergistic effects of cage further significantly improved the antibacterial effect.Ag-TBI-TPE cage has an effective bactericidal effect on E.coli and S.aureus at low concentration(0.5 μM);At high concentrations(10 μM),bacteria can be settled and killed.The Ag-TBI-TPE cage also displayed high biosafety and biocompatibility.(4)A series of aromatic-substituted TPE derivatives were designed and synthesized by introducing high polar substituents(pyridine,thiazole,oxazole)and low polar substituents(benzene,naphthalene,thiophene).TPE derivatives with high polar substituents can be separated and purified to obtain the pure E/Z isomers.It is gratifying to note that each pure E/Z isomers can obtain a single crystal structure,which was confirmed by single crystal X-ray measurement,2D COSY and NOESYNMR spectroscopy.The structure-property relationships of these molecules have been systematically investigated with the combination of spectroscopic methods,theoretical calculations and single crystal data analysis.(5)Five coordination polymers(CPs)with distinct geometries were prepared from pyridinesubstituted TPE derivatives E/Z isomers and silver ion by self-assembly.The different Npositions on the substituted pyridine showed different coordination geometries(lines,chains and metallacycle)and characteristic solid-state fluorescence properties.They displayed reversible mechanochromic behavior in the solid state.(6)The two E/Z isomer of isoniazid-substituted TPE derivatives(TPE-INH-E and TPEINH-Z)were synthesized by Schiff base condensation reaction,which have significant optical properties and different self-assembly behaviors.They were applied to the study of mechanochromism and copper ion detection.The fluorescent method has a fast response speed and high selectivity to copper ions,with a linear range of 0.01-4 μM.