Study On The Synthesis, Separation And Supramolecular Self-assembly Of Cucurbits With High Degree Of Polymerization (n?10)

Cucurbit[n]uril?Q[n]?chemistry has now become an important part of macrocyclic chemistry and supramolecular chemistry.Along with the development of cucurbit[n]uril chemistry,more and more research areas have been found in cucurbit[n]uril chemistry:1)synthesis of cucurbit[n]urils;2)outer-surface interaction of cucurbit[n]urils;3)Q[n]-based coordination chemistry;4)Q[n]-based host-guest chemistry;5)Q[n]-based host-guest-metal ion chemistry.This thesis mainly involed with investigation of synthesis,separation and supramolecular self-assembly of cucurbit[n]urils with high degree of polymerization?n?10?,in particular,the Q[10],including:1)study on the properties of Q[10]itself;2)construction of Q[10]-based porous supramolecular self-assembly in the presence of[CdCl₄]^2?anion as a structure inducer;3)construction of Q[10]-based porous supramolecular self-assembly in the presence of[Cd₄Cl₁₆]^8?anion as a structure inducer,and investigation of its adsorption properties by loading fluorescent dyes to prepare solid fluorescence materials;4)preparation Q[10]-Mⁿ⁺coordination polymers in HCl medium and Q[10]-based supramolecular assembly in HNO₃ medium,and investigation of the process of selectively trapping and releasing metal ions in HCl and HNO₃ aqueous solution systems;5)Based on synthesis separation of cucurbit[n]urils,to explore the synthesis,separation and supramolecular self-assembly of the high degree of polymerization of cucurbituril?n?10?,and develop the application prospect of cucurbituril chemistry in more fields.Using method reported by Professor Liu Simin in Wuhan University of Science and Technology to prepare pure Q[10].Firstly,the water insoluble part of cucurbit[n]urils was isolated,and then dissolved in hydrochloric acid solution,adding amantadine as guest molecule resulted in the formation of white precipitatation?AD@Q[10]?,pure Q[10]can be obtained after removing the amantadine,and confirmed by ¹H NMR spectroscopy using Q[5]as a characteristic guest molecule.Q[10]was used to prepare single crystals of Q[10]-based supramolecular assemblies and coordination polymers by adding different induction reagents and metal cations.Using X-ray single crystal diffractometer determined the crystal structures,and analyzed the possible properties of these assemblies and coordination polymers.Expanding the scale of synthesis to determine their functional properties.The loading capacities of the Q[10]and[Cd₄Cl₁₆]^8-supramolecular self-assembly porous framwork for dyes can be measured by ¹H NMR titration method.Using the TMS as reference substance in solution,the loading capacities of Q[10]-based supramolecular self-assembly for dyes can be worked out.Mixture of the low content cucurbit[n]urils component can be separated and beneficiation from the mixture of cucurbit[n]urils which synthesized by ordinary cucurbit[n]uril synthesis method.Using the column chromatography further separate the mixture of the low content cucurbit[n]urils component.New cucurbit[n]urils could be confirmed by ¹H NMR and mass spectrometry,and the structure was determined by X-ray single crystal diffractometer.