Synthesis Of Materials With Aggregation Induced Emission Properties And Their Applications In Sensing

Materials with aggregation induced emission（AIE）have strong fluorescence in aggregation state or solid state,which is suitable material for the construction of chemical or biological sensors.So,more and more researchers are concerned about it.In this paper,four triphenylamine derivatives with acceptor-donor-acceptor（A-D-A）type were firstly synthesized,and their AIE and mechanochromic fluorescence（MCF）properties have been investigated.Secondly,the luminogens CBI containing carbazole was synthesized.Their AIE properties and applications including pH response and metal ion recognition performance have been studied.Finally,fluorescent compound TPAEBI with triphenylhydrazine and benzoindole was synthesized.Its AIE properties,the recognization properties to cyanide and the responsibility to pH were studied.In the first part,four A-D-A type hydrazone derivatives with triphenylamine were synthesized including p-TPAFB,o-TPAFB,p-TPACFB and o-TPACFB.Their photo-physical characteristics based on substituent properties and their substituent pattern in solution,aggregation and solid state have studied.Intramolecular hydrogen bonding,intermolecular hydrogen bonding and intermolecular charge transfer ability were used to explain AIE and mechanochromic fluorescence properties of luminogens.All of four triphenylamine derivatives presented AIEE effect and the fluorescence intensity of aggregated state increased with 1.07,1.37,9.02 and 8.01 times compared to in pure THF.Ortho-substituted derivatives,o-TPAFB,can form intramolecular hydrogen bonding due to enhancement of intramolecular rigidity,which can lead to the restriction of intramolecule vibrations.And AIEE and CIEE characteristics of o-TPAFB were presented.Steric effect of ortho-substituted trifluoromethyl maked configuration twist and restrictedπ-πinteractions between the intermolecules,so o-TPACFB displayed AIEE and CIEE characteristics.For para-substituted compounds,p-TPAFB and p-TPACFB,can form intermolecular hydrogen bonding in the solid state resulted in the presentation of intermolecular charge transfer,which leaded to mechanochromic fluorescence properties.In the second part,the fluorescence compound CBI containing carbazole and benzimidazole structure was designed and synthesized,and the AIE performance,pH value and metalion response properties were studied.The results showed that the PL intensity of CBI was 1.96-fold in aggregation state compared to in pure THF which presented AIEE effect.CBI displayed pH responsibility with fast,stable and strong anti-interference ability under acidic conditions,which p Ka was 4.74.In addition,presence of Cu²⁺,fluorescence intensity of CBI reduced to 3.70 times accompanying with 37 nm blueshift of the emission wavelength,which can be used as an quenched enhanced by 7.13 times accompanying with 75 nm blueshift in Fe³⁺solution.It can be and the detection concentration was 1～3μM.（3）Fluorescence intensity of CBI was increased by 3.08 times in the presence of Hg²⁺,but the emission peak was redshifted detection limit was 4.76×10^-2μM,and the fluorescence intensity was linear between4.76×10^-2～3μM.（4）Their anti-interference ability to the coexistence of three metalIn the third part,fluorescent probe,TPAEBI of AIE properties containing triphenylamine and benzoindole,was synthesized.The probe displayed colorimetric and fluorescence response to cyanide.The mechanism of TPAEBI in response to the cyanide was determined by Job’s fluorescence analysis,MS spectra experiments and quantization chemical calculation,which cyanide was added to polarized C=N bond of benzoindole lead to neutral compound of formation.When CN^-added to TPAEBI solution,the addition of CN^-destroyed the ICT process of the molecule which leaded to the blueshift of absorption.In addition,TPAEBI was also responsive to pH with p Ka of 8.02 which was suitable pH fluorescent probe in the neutral range.The pH recognition mechanism of the probe was supported by ¹H NMR titration experiments.