Coordination Chemistry Of Ten-member Melon Ring And Construction Of Supramolecular Self-assembling Entity

Following crown ether, cryptand, cyclodextrin, calixarene cucurbit[n]urils,(abbreviated as the Q[n]s or CB[n]s) become a new member in the supramolecular chemistry. Q[n]s(n = 5, 6, 7, 8, 10, 14???) are pumpkin-shaped macrocyclic compounds incorporating a rigid hydrophobic cavity which is accessible via two opposing quasi-planar portals rimmed by carbonyl groups, and they are constructed from n glycolurils bridged by 2n methylene groups. Since the correct macrocyclic structure of Q[6] was elucidated by Mock and coworkers in 1981, there was a rapid development of Q[n] chemistry that included the further isolation and characterization of a series of novel cucurbit[n]urils, such as inverted cucurbit[6]uril(iQ[6]), inverted cucurbit[7]uril(i Q[7]), bis-nor-seco-Q[10](ns-Q[10]), the methylene-bridged glycoluril trimer along with(±)-bis-ns-Q[6] and so on. Q[n]s are able to encapsulate a variety of guest molecules in their central cavities, with the guests bound by non-covalent interactions, in additional, the interaction of Q[n]s with a wide range of metal ions has led to the establishment of Q[n]-based coordination chemistry. Another notable feature of Q[n]s is its rigid molecular structure, and Q[n]s generally have a high thermal stability, and show a high selectivity in molecule recognition. Since the the Q[5], Q[7], and Q[8] homologues of Q[6] were discovered by Day and Kim in2000, cucurbituril chemistry have been greatly developed and shown potential applications in molecule recognition, drug delivery, self-assembled molecular machines, metal coordination chemistry, nano-reactor, and self-assembly of supramolecular materials and so on.The chapter one described a review, including the background of cucurbit[n]urils and their derivatives, researches of cucurbit[n]uril chemistry and potential applications, Q[n]-based coordination chemistry and a introduction of the main contents in this thesis.The chapter two described synthesis and separation of Q[10]: including synthesis of Q[n]s mixture from a reaction of glycouril and paramormaldehyde in acidicmedium; separation of Q[5], Q[8], Q[5]@Q[10] and so on; isolation of Q[10] from Q[5]@Q[10]; at last, structure characterization of Q[10] by NMR and single crystal X-ray diffraction analysis.The chapter three mainly described coordination of Q[10] with Cd2+ cation and its supramolecular assembly in aqueous HCl solution, the crystal structure was characterized by single crystal X-ray diffraction analysis.The chapter four described two supramolecular assemblies based on interaction of Q[5] and Q[8] with [PtCl6]2- through the outer surface interaction of Q[n] in aqueous HCl solutions respectively by single crystal X-ray diffraction analysis, ITC,XRD and so on. Adsorption experiments showed that these two Q[5]-based and Q[8]-based supramolecular assemblies presented between different gases, use five and $ 8 melon platinum ring with the formation of supramolecular self-assembly materials have potential in the different selectivity for different volatile compounds.The chapter five gave a summarization for previous chapters, in particular,supramolecular assemblies based on Q[n]s, and Q[n]-based coordination complexes,and absorption properties for volatile compounds.