The Study Of P-tert-butylthiacalixarene Functional Derivatives

Calixarenes have similar cavity with crown ethers and cyclodextrins, and their size can be accommodated by the control of phenol numbers. There are typical host compounds which are considered as the third generation supramolecular hosters. Thiacalixarene in which methylene bridge replaced by sulfur bond emerged from 1997. The presence of sulfur atoms makes thiacalixarene possess more outstanding features. For example, bridging sulfur itself can take part in coordination in the coordination chemistry which is not existed in classical calixarenes. On the other hand, Schiff bases have been employed widely in the formation of metal complexes. The fusion of the Schiff base and thiacalixarene into a unique entity will give rise to new discovery in metal complexes. Therefore, we initiated the studies of the synthesis of thiacalix[4]arene polydentate ligands, preparation of polynuclear metallic complexes and study of their properties. A series of significant results and developments have been achieved and the main interesting results are as follows:1. p-tert-Butylthiacalix[4]arene was alkylated with N-3-bromopropyl and N-4-bromrobutylphthimide to give thiacalix[4]arene tetrasubstituted derivatives. Then with sucessefully reactions of hydrazinolysis, condensation with salicylaldehyde, 2, 3-, 4-pyridinecarboaldehyde and 2-hydroxy-1-naphthalinaldehyde, a series of 1,3-alternate thiacalixarene Schiff bases were synthesized eficiently. Besides characterizing their structures by 1H, 13C NMR and IR spectroscopy, three single crystal structures were determined by X-raydiffraction method.2. p-tert-Butylthiacalix[4]arene was alkylated with different kinds of chloroalkoxy substituted aromatic aldehydes to give the monosubstituted and tetrasubstituted derivatives. Then a series of thiacalixarene polydentate ligands were synthesized by the condensation with S-methyldithiocarbazate and S-benzyldithiocarbazate. Their structures are characterized by NMR and IR spectroscopy and were further confirmed by X-ray diffraction determination of three representative single crystals.3. By using the above p-tert-butylthiacalix[4]arene and its Schiff base derivatives as polydentate ligands, tens of polynuclear transition metal complexes of p-tert-butylthiacalix[4]arene were prepared. The structures of the prepared transition metal complexes were prelimarily characterized. Two single crystal structures of metal complexes were determined by X-ray diffraction method.