Studies On Synthesis, Characterization And Recognition Properties Of Ferrocene-Based Redox Active Thiacalix[4]Arene Receptors

Thiacalixarenes have been proven to be useful scaffolds for highly preorganized supramolecular receptors. They are widespread applied in many interesting fields such as coordination chemistry, supramolecular chemistry and materials science. The thiacalixarene based receptors possess practical value in the areas of ion transport, molecular switch, electrochemical molecular devices and chemical sensors. This dissertation is an account of the design, synthesis, characterization, and supramolecular recognition properties of novel ferrocene-based redox active thiacalix[4]arene receptors. The main results are as follows:1. The recent research progress of thiacalixarene receptors, including molecular design, chemical synthesis and their applications in the fields of supramolecular recognition and sensing, was briefly reviewed.2. A total of 11 new thiacalix[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 the structures of four compounds being determined by X-ray diffraction techniques.3. The first examples of 1, 2, 3-triazole-linked ferrocene thiacalix[4]arene redox active receptors were synthesized via the CuAAC reaction.4. The supramolecular recognition and sensing properties of these novel receptors were investigated by the cyclic voltammetry and 1H NMR titration techniques. It was found that such receptors have a high selectivity for electrochemical sensing of Eu3+ and H2PO4– ions.5. The crystal structures of two thiacalix[4]arene derivatives were investigated.