Synthesis Of Perylene Diimide Radical ? Derivatives And Application Of Free Radicals In Affinity Substitution Synthesis

In recent years,due to the unique optical,electrical,and magnetic properties,the synthesis,structure,and performance of organic ?-system free radicals and their ?-polymers have attracted much attention.The free radical dimers widely reported before belong to small conjugated systems,and most of them are obtained in concentrated phases.Their stability in air is poor,and there are few studies on environmentally stable free radical ? derivatives.Perylene imide belongs to a larger conjugated system,and if its free radicals generate ? aggregates,it should be relatively stable.Therefore,taking perylene imide derivatives as the research object,a series of perylene diimide free radical ?-polymers were designed and synthesized,and the nucleophilic substitution reaction based on free radicals was discussed.Firstly,using the bended Bisbromoperylene Diimide derivative as the raw material,in the presence of potassium carbonate,using N,N'-dimethylformamide as the solvent,an environmentally stable perylene imide anion radical and The structure of free radical ? polymer has been confirmed by infrared,ultraviolet,XRD and GPC.Due to the localized behavior of free electrons,the free radical properties of Perylene Diimide free radical aggregates are lower than free radicals.Z-scan test found that ?-polymer has high third-order nonlinear optical properties,while the corresponding radicals do not have third-order nonlinear optical properties.At room temperature,the ?-polymer has a multi-radical characteristic that makes its magnetic susceptibility higher than that of free radicals.At the same time,due to the local effect of free electrons,the conductivity of ?-oligomers is lower than that of single radicals,and its conductivity is temperature-dependent.Secondly,based on the above method,when adding a certain amount of ethanol,mono-ethoxy-substituted and di-ethoxy-substituted Perylene Diimide radical dimers were synthesized,and their structures were determined by mass spectrometry,nuclear magnetic,infrared,and XRD.The free radical dimer has strong absorption between 400-600 nm,and has the same electrochemical properties as the single radical.The aggregation behavior in solution is not affected by the concentration of the solution.It can be stable before 200 ? under solid conditions.In addition,it is based on the principle that anionic radicals induce the weakening of aromatic C-Br bond energy.A 1-octyl 7-bromoperylene diimide derivative was synthesized.The molecular structure of the product was determined by mass spectrometry,infrared and nuclear magnetic.In addition,the absorption spectrum of the compound does not change under acidic conditions,but it shows the spectral characteristics of free radicals under alkaline conditions.Based on related literatures,the reasons for this change were further analyzed.