Properties And Applications Of Perylene Derivatives Self-assembly And Metal-organic Framework Assembly

50 years ago,Charles Pedersen discovered the crown ethers,this work is considered as the beginning of the development of supramolecular chemistry.Since then,the field of supramolecular chemistry has progressed greatly,winning two Nobel Prizes and seeing the realization of many applications.A huge number of functional molecules can be applied in supramolecular chemistry,through supramolecular assembly these molecules can construct different structures to meet the needs of various devices.Among many conpunds,perylene derivatives themselves can provide abundant assembly driving forces such as hydrogen bond,?-? stacking and hydrophobic effect,moreover,the molecular properties of this kind of dyes are very stable,which is suitable for the study of supramolecular assembly.The chemical modification of perylene derivatives can realize the balance of assembly driving forces,thus leads to accurate regulation of supramolecular assembly.In this paper,we designed and synthesized multiple perylene carboxyanhydride and-imide derivatives,these perylene derivatives can provide different assembly driving forces and assemble into zero-dimensional or one-dimensional supramolecular constructions.Moreover,the three-dimensional assembly and coordination behavior with metal ions of the oatained perylene derivatives are also reported.So starting from assembly mechanisms,this work develops different supramolecular assembly systems to realize the applications of materials finally.There are mainly three parts as below:1.Recent studies have shown that the kinetically trapped process in self-assembly is similar as traditional polymerization,which are of great significance to study the supramolecular assembly mechanism.To broaden the relevant study of perylene dianhydride(PDA)derivatives,herein,a PDA derivative(TP-PDA)with kinetically trapped self-assembly behavior through a nucleation-growth process in methanol was reported.The transformation of TP-PDA monomers to TP-PDA H-aggregates in accordance with a nonlinear sigmoidal transition,which is characteristic of an autocatalytic process that includes nucleation and elongation processes.The mechanisms were explored,weak intermolecular forces,such as ?-? stacking,hydrogen bonding,and solvophobic interactions,play an important role in the self-assembly process.This study not only presents a new supramolecular assembly system based on TP-PDA,but also inspired us to explore other kinetically trapped supramolecular assemblies that might be easily ignored due to the short trapping time of commonly used experimental timescales.2.To improve the solid fluorescence quantum yield of perylene diimide derivatives(PDIs),a series of imide/bay positions modified PDIs are designed and synthesized to reduce the fluorescence quenching caused by intermolecular stacking.Through special self-assembly method,the PDIs formed high solid one-dimensional microcrystals,and free-standing highly luminescent film can be construted by the microcrystals.The film was conveniently tailored according to practical need,resembling the pH paper.The film can be employed in efficient fluorescent probing of gaseous amines.The fabricated microcrystals show strong solid-state fluorescence(?=38.8%),to our best knowledge its almost the highest value compared with relative PBI crystals.This is also the first report about the sensing of free-standing PDI film.3.In the above work we have studied the self-assembly and material properties of perylene derivatives.To further find potential value of perylene derivatives and broaden the topological structures of perylene derivatives,a first PDI-based three-dimensional metal-organic framework(Zr-PDI)was reportd.Zr-PDI forms a fascinating 3D porous network and can serve as cage to trap electron donors such as organic amines to furnish RAs(Zr-PDI·-)in-situ by photo-induced electron transfer(PET).Being confined in a framework,Zr-PDI·-has superior stability in air and remains intact for at least a month.Zr-PDI·-with intense NIR absorbance,shows an exceptionally high NIR photothermal conversion efficiency(?=52.3%)and good recyclability.The work provides an efficient and simple method towards ambient stable radical anions and affords a promising material for photothermal therapy.