Synthesis Of Novel3,4:9,10-perylene Bisimide Derivatives And Their Applications As Fluorescent Sensor And Catalyst For Knoevenagel Reaction

3,4:9,10-perylene bisimide derivatives have been applied as functional organic dyes, such as fluorescent sensors and fluorescent solar collectors, as a result of their excellent chemical, photo stability and extraordinary photoluminescence efficiency. Meanwhile, the fluorescence of organic amine containing-PBIs is usually quenched according to the PET effect; and it can be enhanced by binding a proton to the N atom in the organic amine. Therefore, these compounds can be used as fluorescent labelling catalysts for some organic reactions.PBI derivatives (Compound2-20,2-22and2-25) have been synthesized by inducing the di-(2-picolyl)amine (DPA) groups into the bay positions of PBIs. These compounds have a very good response to Pd2+compared to other cations in both DMF and CH3CN-H2O systems. And the tested results also showed that there was a good linearity between the fluorescence intensity of compound2-25and the concentrations of Pd2+in the range from0to5μM. The formula y=-23.2437+35.3847x has been obtained by fitting the curve of the relationship between I/Io and [Pd2+].Then, sensor3-12and3-15for Pd2+detection based on the Pd-catalyzed deallylation reaction have been prepared. These compounds also showed higher sensitivity and selectivity for Pd2+detection over other cations in the THF-H2O system. By running a large scale reaction between the sensor3-15and PdCl2under the identical conditions with that has been used for chemical sensing studies, the fluorescence quenching compound3-16has been obtained.By addition, a novel colorimetric and fluorescent senor (sensor4-19) has been synthesized and characterized. It showed higher sensitivity and selectivity toward F-over the other halide ions due to the special cleavage of Si-O bond induced by F-. And the linearity between the fluorescence intensity of sensor4-19and concentrations of F-in the range of0-10μM is extremely good. By fitting the curve of the relationship between [(I586nm0-l586nm)/I586nm] and [F-] the formula y=0.0088+0.84004x had been obtained with a correlation nearly1. Trough the Suzuki coupling and condensation reactions some other PBI derivatives (especially compound5-42) have been synthesized. Compound5-42features a turn-on fluorescent response manner with high sensitivity for Cu2+in the CH3CN system. By running a large scale reaction between5-42and Cu2+in CH3CN a special cyclized product has been obtained. And we speculated that the sensing principle of compound5-42was the special C-N bond coupling reaction on the bay position of PBIs which is catalyzed by Cu2+. Result of the reaction between1-(N-methyl-piperazine)-PBI (compound5-43) and Cu2+further confirmed the principle.Finally, PBI derivatives6-28and6-29which contain organic amines at the imide positions have been prepared and used as fluorescent labelling catalysts to investigate the Knoevenagel reactions between ethyl cyanoacetate and aromatic aldehydes. And these reactions can be tracked by the relationship between the concentration of ethyl cyanoacetate and the fluorescence intensity of reaction solution.