Design, Synthesis And Characterization Of Induced Metal - Cucurbit [Organic] Framework

Cucurbit[n]uril (Q[n]) family, as a new type of macrocycle molecularhost, has been the subject of much interest in recent years because of itsstructural specialties and its potential applications as functional materials.The synthesis and the fundamental properties of Q[n] and thecorresponding host-guest chemistry have been demonstrated by thepioneering works, and have led to their potential applications towardmolecular recognition, molecular switch, molecular device andsupramolecula chemistry.Combination of literature works and the experimental result in ourlaboratory, the Q[n]-based coordination chemistry have been reviewed Ithe details, and also the aim of this thesis is to be establied in constructionof novel Q[n]-metal complexes and corresponding poly-dimensionalsupramolecular assemblies.86Q[n]-metal complexes and theirsupramolecular assemblies are introduced in this thesis.For comparison, the coordination of unsubstituted Q[5] and Q[7]with metal ions were first investigated.14Q[5]-metal and Q[7]-metalcomplexes were synthesized and characterized by single crystal structuralanalysis. The experimental results revealed that Q[5] can include an anionand form a molecular capsule or molecular bowl through coordinationwith metal ions; Q[7] can form only simple complex with metal ions,however, under weak basic medium, a Q[7]-Ag+complex, in which a Ag(H+2O)xcomplex was included, was first synthesized.In the study of the Q[n]-based heterometalic complexes, some novelsupramolecular assemblies were found. It promoted us to establish a newresearch area in the Q[n]-based coordination chemistry, that is theformation of Q [n]-based poly-dimensional supramolecular assemblies inthe presence of the inorganic molecular inducers. In this work,37relatedcomplexes were synthesized and characterized by single crystal structuralanalysis. In particular,20Q[5]-Ln3+complexes were synthesized in thepresence of CoCl2or NiCl2or CuCl2or ZnCl2, amongst of them are10Q[5]-Ln3+complexes which have a two-dimensional network structure. Athree-dimensional framework was established based on the coordinationof Rb metal ions to Q[8] in the presence of the different lanthanide metalions respectively. Moreover,8molecular capsules or one-dimensionalsupramolecular polymers were synthesized based on the Q[5]-basedheterometalic complexes.Finally, it was also investigated that the formation of Q[n]-basedpoly-dimensional supramolecular assemblies in the presence of theorganic molecular inducers and35Q[n] complexes were synthesized andcharacterized by single crystal structural analysis. The experimentalresults revealed that in the presence of organic molecular inducers, suchas p-hydroxybenzoic acid, hydroquinone, p-hydroxybenzonitrile andp-nitrophenol,22Q[5]-metal complexes were synthsised with mainly five structural models: Q[5] pairs; a one dimensional supramolecular cahinthrough hydrogen bonding; a one dimensional supramolecular polymerthrough direct coordination of metal ions to the Q[5]s with or without theorganic inducer; a one dimensional helic supramolecular polymer.