| Calixarene, the third generation supermolecular host compound, has attracted considerable attention in the field of supramolecular chemistry in recent years, due to their synthetic availability, tunable cavities, and unique conformational features. Calixarenes not only have strong coordination ability of metal ions or other positive ions, but also can capture neutral molecules to form the host-guest complexs. In order to achieve complexing (capturing) a specific 'guest' molecule (ion), designing and synthesizing the new types of 'host' molecules with unique structures to recognize specific 'guest' molecules (ions) is necessary. In this work, we designed and synthesized a series of new derivatives of oxacalix[n]arene with functional groups on the neucleophilic aromatic rings, and investigated their coordination-driven and hydrogen bond-directed self-assembly capabilities.1. Four oxacalix[n]arenes with nitrogen atoms which were positioned on the outer edge of the cavities and favored to interact with metal ions, was synthesized by2,6-dichloropyrazine,4,6-dichloropyrimidine, catechol and resorcinol. Studies on the formation of 'metollosupramolecular structures' by these oxacalixarenes have been carried out, and found these compounds could interact with Ag+, Cu2+, Zn2+,Pd2+ions and form0D,1D and2D supramolecular complexes.2. Twenty-one new oxacalix[n]arenes with functional groups such as carboxylic acid, amine, hydroxyl, and pyridyl functions were synthesized. They were characterized by1H-NMR,13C-NMR and HRMass analysis. Compound3.12can self-assemble into an unprecedented six-fold interpenetrated diamondoid network via intermolecular hydrogen bond interactions in EA.3. Calixcrown, a new type of host molecule which combined the characteristics of calixarenes and crown ethers was synthesized. We obtained11calixcrowns and analogues and confirmed by1H-NMR,13C-NMR and HRMass analysis. Thereinto, Oxacalix[2]arene[2]pyrazine-crown-7(3.58) could be threaded by dibenzyl ammonium ion.
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