Synthesis Of Methyl-substituted Cucurbit Rings And Study On The Properties Of Supramolecular Self-assembly

Cucurbituron,also known as cucurbituron,is one of the important research directions in the field of supramolecular chemistry,and its chemical formula is Q[N].However,due to its special properties,it has not been able to make breakthroughs in the research due to its functional modification.Since Japan replaced the alkyl of cucurbituron the last century,the cucurbituron with controllable function was obtained,which pointed out a new direction for the research and development of cucurbituron.Among them,the most controllable and best function is the separation of water-soluble and organically soluble methyl cucurbituron through the synthesis of methyl glycylurea diether and common glycylurea,which not only broadens the application prospect of supramolecular compounds,but also enriches the research content in coordination chemistry.Q[n]s has different chemical properties due to different coordination between carbonyl group and metal ions,so different functional materials can be prepared according to different properties.After more than ten years of development,cucurbituron coordination chemistry has made great breakthrough,and through the outer wall interaction and port interaction between cucurbituron and metal,we have designed polymers based on cucurbituron metal supramolecular,which has become a new research direction in cucurbituron coordination chemistry,including the following four types:1)The cucurbituron metal coordination polymer was synthesized by using the electron pushing effect of substituted alkyl groups on the outer wall of cucurbituron,2)The metal organic coordination polymer was synthesized by the interaction between the aromatic ring and the outer wall of the cucurbituron in the inducer;3)the metal coordination polymer was formed by the interaction between the inorganic anion and the outer wall of the cucurbituron;4)the metal organic polymer was formed by the coordination of the hydroxyl Group on the outer wall of the cucurbituron.On the basis of previous research results and experimental experience,the research scope of cucurbituron supramolecular compounds was broadened by improving the reaction conditions,and a series of supramolecular self-assembly experiments of modified hexamethyl cucurbituron and trans hexamethyl cucurbituron were carried out,The specific research conclusions include the following aspects:1)in the aspect of synthesis and separation,we synthesized mixed methyl cucurbit ring by methyl glycylurea diethyl ether and common glycylurea,and then changed the separation conditions of mixed methyl cucurbituron,we shortened the synthesis and separation cycle of Me₆Q[3,3]and i Me₆Q[3,3].2)In the construction of Me₆Q[3,3]supramolecular self-assembly experiment,a series of supramolecular self-assembly of Mg²⁺,Ca²⁺,Sr²⁺and Ba²⁺under the condition of inducer[Cd₂Cl₈]^4-,or[Cd₂Cl₇]^3-,[Cd Cl₄]^2-were synthesized with Me₆Q[3,3]as the main body.3)In the construction of Me₆Q[3,3]supramolecular self-assembly experiment,the interaction between Me₆Q[3,3]and alkali metal cations under different inorganic salts as structure inducing reagents was studied.It was found that the complexes containing K⁺,Cs⁺,Rb⁺cations would appear under cadmium chloride anions such as[Cd₂Cl₈]^4-,[Cd Cl₄]^2-,However,according to the experimental phenomenon,the complex containing Na⁺cation will not be produced.4)The interaction between rare earth metals(Ln³⁺=La³⁺,Lu³⁺,Ce³⁺,Pr³⁺,Eu³⁺,Gd³⁺)and i Me₆Q[3,3]via structure inducer was studied.Under the conditions of zinc chloride,hydrochloric acid and rare earth compounds,the interaction between i Me₆Q[3,3]and Ln³⁺cation led to the formation of metal organic complexes based on i Me₆Q[3,3],Among them,Zn²⁺cation forms[Zn₂Cl₈]^4-or[Zn Cl₄]^2- anion as structure inducing reagent.