The Construction Of Supramolecular Polymers Based On Pseudorotaxane Unit And Their Functions

Supramolecular chemistry focuses on ordered aggregates with well-defined microscopic structures and macroscopic properties fabricated by two or more molecules relying on oriented intermolecular interactions（coordination bonds,hydrogen bonds,electrostatic interactions,π-πstacking,hydrophilic/hydrophobic interaction,Van der Waals forces and so on）with certain matching relationships.With the depth of research on the mechanism of intermolecular interactions and the strong desire for molecules owning complicated conformation and function,supramolecular chemistry has developed rapidly in recent decades.Self-assembly,folding,molecular recognition,and host?guest chemistry were hence raised as novel concepts.Based on host-guest recognition,and sensitive response to external stimuli.Up to now,scientists have utilized rotaxane,pseudorotaxane,and catenane to synthesize a series of linear,hyperbranched,star-shaped and network supramolecular polymers with self-healing,energy storage,degradation control,photocatalysis,targeted drug delivery and so on.These characteristics results their immense potentiality in smart materials,information storage,molecular machines,self-healing materials and drug delivery.More attention to the supramolecular polymers focuses on novel topological structure,while the research on their functional applications is still weak.In this dissertation,we introduced fluorophores,metal complex,polyoxometalate（POM）and covalent bond polymers into polyrotaxane systems to gift responsed supramolecular polymers controllable optical,electrical and mechanical properties.This dissertation has done the following works in detail:1、Two asymmetric conjugated monomers AB2-1 and AB2-2 with dibenzo-24-crown-8 and dibenzylamine groups were successfully synthesized.We have explored the formation of their supramolecular hyperbranched polymers through host?guest recognition controlled by pH.The controllable construction of vesicles and micelles was realized,and the relationship between polymerization and fluorescence was revealed.2、Cis and trans tetraphenylethylene derivatives E/Z-2DBA-TPE,exhibiting aggregation induced luminescence（AIE）,with two secondary ammonium salts and the TPE derivative 4DB24C8-TPE with four crowns were synthesized.When they were titrated with acid into a THF solution of 4DB24C8-TPE,viewing emission bands were blue shifted by 67（E-2DBA-TPE）and 38（Z-2DBA-TPE）nm respectively,and synchronously the fluorescence intensities increased significantly with a factor of 157 and 97.Herein,the E/Z isomerization effect can be distinguished clearly.This picture shows obvious cis-trans isomerization effect in the recognition process.The present supramolecular system based on TPE stereoisomers displays tunable photophysical properties and morphological features.3、We synthesized A₃ with three dibenzo-24-crown-8（DB24C8）groups and poly（?-caprolactone）s（PCL）with two and four DBA-terminated arms（2-PCL-DBA and 4-PCL-DBA）.Two networks were constructed by hierarchical self-assembly（metal coordination and host-guest recognition）,and realized multi-level regulation supramolecular metal gels.4、We have introduced polyoxometalates（POM）into host?guest systems and synthesize quasi-rotaxanes based on secondary ammonium salts/dibenzo[24]crown-8to prepare a supramolecular polymer network.This unique mode can construct two-dimensional ion channels,generating outstanding controllable proton conductivity.For the first time,secondary dialkylammonium salt/crown ether[2]pseudorotaxanes are utilized as a proton conductor.This paper has expanded the applications of supramolecular polymers by introducing functional molecules.Promising future of supramolecular polymers is predicable in organic photoelectric materials,self-healing gels,proton conductive materials and hybrid materials.