Synthesis And Gelation Properties Of Tetrathiafulvalene Organic Gel Factor With Amide Group As Hydrogen Bond Source

The low molecular weight organogel refers to a soft substance in which a relatively low molecular weight organogel factor is assembled in a solvent by a plurality of intermolecular multiple weak interactions to form a nano or micro fiber structure encapsulating solvent.At present,the design of simple and novel low molecular weight organogel factors,the discovery of new nano or micro-assembled structures and the understanding of the relationship between the structure and properties of molecules,deepening the understanding of the self-assembly of soft materials to form colloidal materials,is A hot spot in the study of supramolecular gels.Since tetrathiafulvalene(TTF)and its derivatives have good electron-donating properties and molecular configurations as planar structures,they can induce ?-? stacking between molecules and interactions such as S...S.In this paper,two series of small molecular weight gelling factors containing tetrathiafulvalene structural units were designed and synthesized,and their gelation behavior,dry gel self-assembly morphology and structure in various organic solutions were investigated in detail.Thereby finding the intrinsic law between the molecular structure or shape and the self-assembled aggregate structure.The main research contents are:1.A series of T-type organogel factors with pyridazine and tetrathiafulvalene crown ether structure was synthesized.T-type molecules can enhance the ?-? stacking between molecules;crown ether can form a supramolecular gel system with multiple stimuli response through the recognition of host and guest with organic ammonium salt.The effect of the difference in the length of the terminal alkyl chain of the T-type molecule on the self-assembled structure was further investigated.The results demonstrate that the ability of the target compound to form a gel depends largely on the length of the alkyl chain on the amide group at the end of the molecule.The longer the alkyl chain,the stronger the ability to form a gel;it can be involved in electron-deficient F4 TCNQ.A charge transfer complex gel was formed in the solvent;the morphology of the gel formed by the compound was observed by FE-SEM including fiber aggregation,rod shape and spiral structure.2.A series of compounds having a tetrathiafulvalene cyanobiphenyl unit structure was synthesized.Such compounds are typical compounds having a D-?-A molecular structure.Tetrathiafulvalene is a typical electron donor,and the cyanobiphenyl unit is a typical acceptor unit.The two parts are grouped together to form a compound of D-?-A molecular structure through spacers of different lengths.The length of the spacer was varied to study the difference in gel formation of the compound during self-assembly.The results demonstrate that the ability of the target compound to form a gel depends largely on the length of the spacer in the D-?-A molecule.The shorter the spacer,the easier it is to form a gel;the charge can be formed in the solvent with the electron-deficient F4 TCNQ.The composite gel was transferred;the morphology of the gel formed by the compound was observed by FE-SEM,including spherical and tubular.Above two types of gelling factors,FT-IR indicate that intermolecular hydrogen bonding interactions are the main driving force for gel formation;small angle X-ray diffraction studies indicate that the gels formed are arranged in a layered structure;Multiple stimuli response behaviors such as temperature,chemical redox reactions,trifluoroacetic acid-triethylamine stimulation.