Studies On Synthesis, Characterization And Recognition Properties Of Ferrocene-Based Redox Active Calix[4]arene Multisite Receptors

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 progress of calixarene based redox-active receptors, including molecular design, chemical synthesis and their electrochemical recognition and sensing properties, was briefly reviewed.2.A total of 12 new calix[4]arene derivatives were successfully synthesized. Their structures were fully characterized by elemental analysis, IR, ¹H NMR, ¹³C NMR and MS spectroscopies, as well as for two molecules being determined by X-ray diffraction techniques.3.Three new amide-linked ferrocene calix[4]arene open-chain multisite receptors were synthesized by the selective O-alkylation, reduction and acylation reactions.4.Novel amide and 1, 2, 3-triazole-linked ferrocene calix[4]arene multisite receptors were synthesized via click reaction as a key step in excellent yields.5.The recognition and sensing properties of these novel calix[4]arene based receptors were investigated by the cyclic voltammetry and UV-vis techniques. It was found that they show a high selectivity for sensing of Cu²⁺ and H₂PO₄^- ions.