Functional Modification And Transition Metal Complexes Of Thiacalixarene

Calixarene is one kind of macrocyclic compounds derived from the condensation of phenol with aldehyde. With ease of synthesis, much more functionality, persistent shape and size as well as easily chemical modification calixarenes are named as the third generation supramolecular hosters and have been used as the platforms for so many types of chemical researches. From 1997 thiacalixarene in which methylene bridge replaced by sulfur bond has been recognized and quickly become new 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. The presence of sulfur atoms in place of the usual CH2 bridges makes thiacalix[4]arenes very interesting molecules, with many features that are not present in the chemistry of''classical''calixarenes. It is now obvious that these compounds possess some very uncommon features, different conformational preferences, and special complexation properties, and thus have many potential applications. In this work we studied the synthesis and complexing properties of some functional thiacalixarnes and have maken a series of significant and creative results. The main results are showed as follows:1. A series of functional thiacalixarene derivatives has been synthesized by some carefully designed efficient procedures. Their structures are characterized by NMR and IR and elemental analysis, and confirmed by X-ray diffraction determination of eight representative single crystals.2. p-tert-Butythiacalixarene reacted with excess toluenesulfonyl chloride to give only two phenolic hydroxyl sulfonylated products. In the system of K2CO3/KI/acetone thiacalixarene can be fully alkylated by versatile alkylating reagents to give oxyacetate, chloropropyl, cyanopropyl and amide derivatives in moderate yields. The amide derivatives can be also prepared by ammonolysis of ethyl thiacalixaryl acetate with excess aliphatic amines and hydrazine in refluxing ethanol. Aliphatic diamine can give selectively one amine products or cyclic amides according to properties of alkylene groups. By the oxidation of acidic hydrogen peroxide the sulfonyl bridged calixarene derivatives can be prepared in high yields.3. Thiacalixarene polydentate Schiff bases, hydrazone and ketoimine ligands can be easily prepared by the condensation of thiacalixarene amides bearing with terminal amino groups with pyridinecarboxaldehyde, salicyladehyde or ferrocenylβ- diketone. The coordination reactions of these polydentate ligands with some transition metal ion to form multinuclear metal complexes have been studied. The determination of structures of these complexes needs further research.