Construction Of Hydrogen-bonded Organic Framework Of Aminium Sulfonate And Its Application

Since the construction of metal-organic framework materials and porous coordination polymers with porous network structures by metal cations and organic molecular ligands was reported,the construction of crystalline materials with ordered structures by intermolecular forces using organic small molecule ligands has attracted intense interest and attention,and is widely used in the fields of selective gas separation/storage,proton conduction,catalysis,molecular recognition,optics and biomedicine.These include hydrogen-bonded organic frameworks(HOFs),supramolecular organic frameworks(SOFs),porous organic salts(POSs),porous molecular crystals(PMCs),or organic crystalline materials(COMs).Compared with other pore materials,hydrogen-bonded organic framework materials have their own inherent advantages such as unique solution processability,high crystalline structure,good recyclability,and easy purification,but also due to the characteristics of flexible hydrogen bonding and weaker bond energy usually make HOFs fragile and difficult to maintain permanent pores,which greatly hinders the development and application of such materials.Therefore,the development of stable and high-performance hydrogen-bonded organic framework materials has become a popular research proposition in the field of energy materials in the new era.In this thesis,we synthesized hydrogen-bonded organic framework materials with different structures using organosulfonic acid and organic amines as ligands,and designed materials with different conformations by changing the dissolution environment of the ligands(adjusting the p H of the solution or adding different templating agents).Two organocrystalline materials with different configurations,FJU-362 and Crystal 9,were constructed using 1,5-naphthalenedisulfonic acid and 4,4’-sulfonyl diamine,and the differences in proton conduction properties depending on the degree of protonation were investigated,and the mechanism of proton conduction was demonstrated by structure and solid-state NMR.Subsequently,we skillfully constructed a stable hydrogen-bonded organic framework material FJU-360 by charge-assisted hydrogen bonding using sunset yellow and terephthalimide as synthons.The material possessed a fluorescence intensity much stronger than that of the single ligand,while showing a sensitive response to aniline,and through calculations,we revealed the intrinsic mechanism of the variation of the fluorescence intensity of the material with the concentration of aniline.Finally,we successfully obtained a hydrogen-bonded organic framework FJU-351 by assembling 1,5-naphthalenedisulfonic acid and triphenylmethylamine in methanol solution using hydrophobic solvent drive,and we investigated the performance of the material without thermal concentration of hydrogen peroxide by column chromatography because FJU-351 possesses the property of "water self-healing" in air.The performance of the material was investigated by column chromatography.The sulfonic acid ligands involved in the paper include 1,5-naphthalenedisulfonic acid,sunset yellow,and organic amine ligands including 4,4’-sulfonyl diamine,triphenylmethylamine and terephthalimidamide(hydrochloride).Five crystalline organic materials were synthesized by self-assembly.The rich selection of ligands further expands the synthetic subapplications of hydrogen-bonded organic framework materials and also enriches the crystal network engineering.We have characterized the crystalline materials using single crystal X-ray diffraction,X-ray powder diffraction,Fourier transform infrared spectroscopy,thermogravimetric analysis,and elemental analysis,and studied the properties of proton conduction,segregation,and fluorescence response of the materials according to different structures,and further analyzed the application mechanisms.