Functional Modification And Application On Nanomaterial Of Resorcinarenes

As the third generation supramolecular hosters, calixarenes have been used as the platforms for so many types of chemical research. Resorcinarenes and pyrogallol[4]arene represent an important class of synthetic host molecules and have versatile applications in supramolecular chemistry such as complex extraction, molecular devices, molecular recognition, self-assembly and nanomaterials. Even if attracted much attention and achieved some important progress, the application of functional resorcinarenes on preparation of naomaterial remains as one o f much potential valuable research fields. In this thesis we initiated the studies of the synthesis of functional polydentate ligands based on resorcinarene and pyrogallol[4]arene, and aminoresorcinarene with eight amino groups as the fabrication of gold hydrosol. A series of the significant results and developments have been achieved and the main interesting results are as follows:1. Reaction of tetraakyl resorcinarene oxyacetates reacted first with diamines, hydrazine to give resorcinarene amide, hydrazone derivatives, which in turn condensated with salicylaldehyde, pyridinecarboxaldehyde to yield several types of Schiff derivatives. Besides characterizing their structures by NMR and IR, UV-vis and elemental analysis, the single crystal structure of one representative ester was determined by X-ray diffraction method.2. An aminoresorcinarene with eight amino groups as a novel ligand was used as stabilizer for fabrication of gold hydrosol. The aminoresorcinarene-capped gold nanoparticles were characterized and analyzed by the ultraviolet visible spectroscopy (UV-vis), Fourier transmission infrared spectra (FT-IR), X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. The experiment showed that nearly ten times of the usual amount of hydrate hydrazine as a reducing agent needed to be used, and the obtained TOMR-stabilized gold hydrosol had a higher level of stability at room temperature, which might be related to the structure of aminoresorcinarene molecule and the formation of hydrophilic double layer structure of aminoresorcinarene on the surface of gold core.3. Under microwave irradiation aryl pyrogallol[4]arenes have been efficiently synthesized in excellent yields by cyclocondensation of pyrogallol with aromatic aldehydes and their alkylation reactions with some alkylating reagents such as n-butyl iodide, benzyl chloride and ethylα-chloroacetate were also finished quickly and efficiently to yield fully O-alkylation products. These green routes provide fast, simple, high-yielding, energy-efficient and non-polluting synthetic methodology for functional aryl pyrogallol[4]arenes. The structures of aryl pyrogallol[4]arenes were affirmed by spectroscopy and X-ray diffraction determination of six representative compounds.