Preparation And Properties Of Hydroxylated Perylene Imide Derivative Radical Anions

Delocalized radicals based on conjugated systems have many excellent physical properties,and are very sensitive to various external stimuli such as light,electricity and magnetism.Organic semiconductors and organic conductors are obtained by controlling the molecular structure and spin interaction,which have certain application potential in organic spintronics,information storage,biological probes and other directions.At present,the bottleneck of radical application is still poor stability.Therefore,this thesis takes the highly electron-deficient perylene diimide（PDI）as the basic structure,designs and prepares environmentally stable perylene diimide radical anions through optimized.First,this thesis introduces asymmetric electron-withdrawing substituent group（bromine atom on one side and hydroxyl on the other side）at the bay position of the perylene imide perylene nucleus.On the one hand,the existence of electron withdrawing groups reduces the reduction potential of the perylene imide.,It is easier to form radical anions;on the other hand,the introduction of hydroxyl effectively reduces the distance between the donor and the recipient,monohydroxyperyleneimide（ABrPDI-OH）can form intermolecular hydrogen bonds with DMF,and then generate peryleneimide radical anions(ABrPDI-OH^·-)through photoinduced intermolecular electron transfer.The force between ABrPDI-OH and DMF is big enough so that ABrPDI-OH^·-can exist stably in the solid state,so that ABrPDI-OH^·-can be characterized by EPR,NMR and other means.Secondly,changing the ratio of TCM and DMF or changing the pH value can realize the mutual conversion of ABrPDI-OH and ABrPDI-OH^·-,accompanied by solvatochromism.According to the literature,it is known that hydrogen ions can protonate the nitrogen atoms on DMF and hinder the intermolecular electron transfer process from DMF to ABrPDI-OH,ABrPDI-OH^·-cannot be formed.Then we applied this to the colorimetric sensor to detect heavy metal ions,the detection limit of Fe³⁺was 1.38 ppm,and the response time was 1minute.In addition,The unique deprotonation reaction of Abr PDI-OH with organic bases is also accompanied by solvatochromism.Based on the color change of abrpdi Oh caused by organic base,a new colorimetric sensor with high sensitivity and fast response for specific volatile organic amine was prepared.In the detection of organic amines by UV/Vis spectrum,ABrPDI-OH has the best detection effect on triethylamine,and the detection limit can reach0.043 ppm.