Synthesis Of Ring Expansion Perylene Imide Derivatives And Their Anion-? Interactions

"Anion-? interaction"-a kind of intermolecular non-covalent weak force,is used to describe the interaction between the positive quadrupole ? systems and anions.Due to the extensive exists in natural systems,it has attracted more and more attentions from scientific researchers in different researching areas.Perylene Diimide derivatives(PDI)has two electron-withdrawing imide groups,however the electron density on its ? systems is still greater than that on naphthalene diimide derivatives(NDI),thus,PBI could only 'interact with strong basic anions while cannot interact with weak basic anions,it restricts the application of PBI in many fronts.Here,we are aiming at designing and systhesizing a series of stable PBI with a more electron-deficiency ? system.Based on the classical Diels-Alder reaction,we start from 3,4,9,10-perylene tetracarboxylic acid anhydride to design and synthesis several benzoperylene bisimide derivatives,i.e.,benzoperylene bisimide derivatives(PTI),chlorobenzoperylene bisimide derivatives(PTI-Cln)and dibenzoperylene bisimide derivatives(PHI).All of the compounds have been characterized by NMR spectra,mass spectra,UV-Vis spectra.Some of their structures have been obtained by X-ray single crystal diffraction experiments.Compared to PDI,the electron-deficiency for ?-planes of PTI and PTI-Cln increase slightly confirmed by anion-? experiments conducted between ?-acids and different kinds of anions investigated by UV-vis spectrometer,i.e.,PTI and PTI-Cln could give spectral responses when weak basic anion I-is added.Even,for PHI,the electron density of its ?-plane is extremely deficient than that of PBI,i.e.,PHI could respond to almost all kinds of anions on spectrum except for non-basic anions such as PF6-etc...Several other analysis methods include NMR titration,etc.were futhur used to confirm that the interaction patterns between compounds and different anions are not the same.