The Supramolecular Assembly Base On Perhydroxylated Cucurbit[6]uril With Keggin Type Heterpolyacids And Their Functional Properties

The cucurbit[n]urils?Q[n]s?are a new type of macrocycle and cage molecular compounds.It's hydrophobic cavity can enwrap organic compound and polar carbonyl groups of portals rimmed can interaction with metal cation or othe positive matter.Moreover,the cucurbit[n]urils'outer–surface has a strong positive charge,which can have the outer outer–surface interactions with anions or othe negative matter..The solubility of general cucurbit[n]urils is poor which be confined study to cucurbit[n]urils'chemistry,as a result,more and more attention are taken on modified cucurbiturils.Heterpolyacids?HPAs?,also known as Polyoxometalates or metal oxide clusters anion,are composed of two or more inorganic oxygen acid condensation.Haveing both acidic and redox properties,they can soluble in water and other oxygen-containing organic solvents.have showed a good prospect in the fields of catalytic,recognition,isolation and adsorption as functional materials with their unique structure and outstanding properties.Literature and previous work indicate that the supramolecular self-assemblies of cucurbit[n]urils?Q[n]s?and heteropolyacid?HPAs?based on the outer-surface interaction of cucurbit[n]urils not only remains the original construction features of cucurbit[n]urils and heteropolyacids,but also remains the multifunctional features of heteropolyacid such as acidity,catalysis,oxidation and so on.The driving force is attributed to the ion-dipole interaction of positive electro-potential outer surface of Q[n]s with heteropolyacid anions.In this paper,perhyoxylated Q[6]?OH?₁₂Q[6])and Keggin type HPAs,H₃PMo₁₂O₄₀(PMo₁₂),H₃PW₁₂O₄₀(PW₁₂)and H₄SiW₁₂O₄₀(SiW₁₂),are selected as building blocks,?OH?₁₂Q[6]-HPAs supramolecular assemblies will be synthesized and characterised,and their functional properties,such as catalysis,adsorption,recognition,isolation and and so on will be studied in detail,respectively.In this work,the perhydroxylated cucurbit[6]uril{?HO?₁₂Q[6]}were selected as building blocks,and different solid single crystals were collected in 3.0 mol and 6.0 mol HCl aqueous solutions,respectively.he single crystal X-ray diffraction analysis shows that the two kinds of?HO?₁₂Q[6]are slightly different.At the concentration of these hydrochloric acids,porous compounds?A and B?,A at 3 M,and B at 6 M.are obtained.Unlike the previously reported Q[n]-based porous compounds,which usually exhibit a preference for methanol adsorption,these porous compounds have a good selectivity for polychloromethane.In the present work,perhydroxlated cucurbit[6]uril{?HO?₁₂Q[6]}and Keggin-type HPAs,such as H₃[PMo₁₂O₄₀],H₃[PW₁₂O₄₀]are selected as the basic building blocks,the interaction of?HO?₁₂Q[6]and the selected HPAs gave two types of supramolecular assemblies under different HCl concentrations|:hybrids of?HO?₁₂Q[6]with the selected HPAs anions were obtained from?HO?₁₂Q[6]-HPAs-HCl?1M?systems,whereas?HO?₁₂Q[6]-based supramolecular assembly without POM species was obtained from?HO?₁₂Q[6]-HPAs-HCl?6M?systems.This process may offer a route to uptking and release HPAs.Moreover,the?HO?₁₂Q[6]/HPAs-based supramolecular assemblies exhibit catalytic activities for esterification and degradation of aqueous dyes;adsorption properties for volatile organic compounds or different fluorochromes,yielding solid-state adsorbing materials or fuorecent materials;photochromic properties upon photochemical response of color changes.