Syntheses And Properties Of Calix "4" Arene Derivatives With Ferrocene Groups

Regarded as "the third supramolecular receptor" along with crown ethers and cyclodetrins, calixarenes are a class of well defined macrocyclic oligomers of phenols bridged by methylene groups. Owing to their unique three-dimensional cavities, convenient preparation in large quantities, versatile complexation and recognization abilities towards ions or molecules, they have received considerable attentions in recent years. Due to easy modification on both lower and upper rims, the parent calixarenes frequently serve as molecular scaffolds for the construction of more elaborate supramolecular systems. The supramolecular electrochemical recognition based on redox-active receptors is a new emerging topical area of supramolecular chemistry. It is greatly important to both field of supramolecular chemistry and practical domain of advanced techniques such as ion transport, molecular switches, electrochemical molecular devices, and chemical sensors. Therefore, an investigation on design, synthesis and supramolecular properties of calix[4]arene multisite receptors containing ferrocenes as redox-active probes was systematically carried out. The main results are as follows:1. The recent research progess of calixarene based redox-active receptors, including molecular design, chemical synthesis and their electrochemical recognition and sensing properties, was briefly reviewed.2. Organic-inorganic hybrid supramolecular complex was designed and synthesized. It was proved that complexes containing Cu in electron pairs, no single electronic structure, indicating the presence of Cu complexes in the form of Cu (I).3. Two new type of ferrocene-based calix[4]arene receptors were designed and synthesized, which ferrocene was electrochemical active center. Cyclic voltammetry and UV spectra showed that these compounds have a good effective of electrochemical response to the series of cations and anions, as well as the recognition and sensing properties of the compounds to the series of ammonium anions.4. Chiral calix[4]arene receptor containing amino acid fragment were designed and synthesized.The UV spectra show that the compounds have a good capacity to match with metal cation. Especially to Na+,K+,Ag+,Zn2+,Cd2+ and other transition metal and alkali metal ions.