Construction And Application Of Macroporous Functional Supramolecular

Organic dyes,as a kind of environmental pollutants,widely exist in all fields of the environment.Due to their complex mechanism on environmental pollution,long residual time,difficult degradation,and strong teratogenicity,mutagenicity and genotoxicity to human body,organic dyes need to be given priority in environmental monitoring.Based on the current situation that pollution status and sources of organic dyes in the Environment,a novel category of cuboctahedral supramolecular cages with large size,large confined cavities and some functionalizations inside or outside are designed and synthesized in this thesis,which was combined with designability,host guest recognition and multi-stimulus response of supramolecule structures.Specific recognition of organic dyes pollutants can be achieved by making use of hydrophobic interaction,electrostatic interaction,π-πconjugation and other non-covalent bonding interactions existed in the restricted cavities of these functionalised supramolecules.This special host-guest recognition is similar to the binding of natural biomolecules and guest molecules（such as antibodies and antigens）.Combined with high sensitivity output modes such as fluorescent signals or electrical signals,the artificial supramolecular sensors with high sensitivity and selectivity for organic pollutants such as polycyclic aromatic hydrocarbons can be constructed,which are comparable to natural enzymes or antibodies.At the same time,the introduction of a catalytic guest into the supramolecular cavity and the use of the charge andπ-πconjugation are expected to achieve the recognition and catalytic degradation of pollutants.It includes the following three parts.（1）Synthesis and characterization of functional supramolecules with recognition of porphyrin-like photocatalysts.In this part,the terpyridine-based octahedral supramolecular cage S1 and S1’including imidazole salt were designed and synthesized,and the ¹H NMR,¹³C NMR,2D COSY,2D NOESY,ESI-MS,TWIM-MS,TEM and other methods were used to characterize their structure and prove the formation of their structure.By investigating the host-guest properties of this new type of supramolecular cage,the supramolecular cage S1 can interact specifically with the porphyrin photocatalyst,and the single porphyrin molecules with a large conjugated plane are uniformly dispersed into a single supramolecular cage,which solves the problem of reduced catalytic efficiency of porphyrin photocatalysts due to their tendency to aggregate.Moreover,the restricted cavity of the supramolecular cage can adsorb or encapsulate Organic dyes pollutants,which can confine the porphyrin photocatalysts and Organic dyes pollutants in a small nanocage,thereby significantly increasing the collision probability between photocatalysts and Organic dyes contaminants,and it is expected to enhance the efficiency of porphyrin photocatalysts in degrading Organic dyes contaminants.（2）Synthesis and property exploration of functional supramolecules,based on triphenylamine functional groups.Firstly,organic ligands L2 and L2’with imidazoly triphenylamine functional groups,as well as cage-like cuboctahedral supramolecular S2 and octahedral S2’,were designed and synthesized.¹H NMR,¹³C NMR,2D COSY,2D NOESY,ESI-MS,TWIM-MS,TEM and other characterizations were performed to confirm the formation of this structure.In addition,a series of properties of supramolecular S2 were explored:1)Based on the electron-supply characteristics of triphenylamine,the electrochemical properties of ligand L2 and supramolecular S2 were explored,and the results showed that ligand L2 and supramolecular S2 could be reversibly oxidized,and their electrochemical activities were similar,which could be used in wastewater treatment,environmental monitoring and other fields.2)Based on the large cavity structure of S2（7.04 nm）,the use of host-guest recognition was explored,and it was found that S2 can also combine a 5,10,15,20-tetra（4-hydroxyphenyl）porphyrin,thereby separating the photocatalysts with porphyrins from the aggregation state,and increasing the specific surface area of the catalyst,thus improving the catalytic efficiency of pollutants in the environment.3)The interaction between supramolecular S2 and the organic dye isocyanate was discovered through nuclear magnetic characterization,which provides a new idea for supramolecular S2 to detect organic dyes in the environment.（3）Exploring the effect of the change in position of fluorescent functional groups on the synthesis of functional supramolecular structures.By changing the position of functional groups（triphenylamine,naphthalene）in the first and second part of ligands,the imidazoly triplepyridine ligands L3 and L4,as well as the three-dimensional supramolecular cages S3 and S4,were designed and synthesized,and a series of characterizations were performed to confirm the formation of this structure.The results show that changing the substitution position of functional naphthalene or changing the position of the connected triphenylamine functional group can form a cubic octahedral structure without affecting the assembled supramolecular structure,which expands the diversity of functional supramolecular materials.