Studies On Synthesis And Properties Of Thiacalix[4]arene-Based Acyclic And Macrocyclic Crown Ether Receptors

Thiacalixarenes have attracted much attention in recent years largely due to their unique three-dimensional cavities, chemical diversity and specific affinity towards cations, anions and neutral molecules. These novel features make thiacalixarenes very promising scaffolds in the design of highly preorganized supramolecular receptors. Thiacalixarenes are greatly significant to the field of supramolecular chemistry and practical domain of advanced techniques such as ion transport, molecular switch, molecular devices as well as chemical sensors. The design and synthesis of a variety of optical and redox active receptors is a challenging topic in supramolecular chemistry. However, there is a paucity of use of thiacalixarenes as building blocks to construct fluorogenic and electrochemical sensors. This dissertation is an account of the design, synthesis, and supramolecular properties of novel thiacalix[4]arene-based acyclic and macrocyclic crown ether receptors. It is divided into three sections.The first part briefly reviews the recent research progress of thiacalix[4]arene-based acyclic and macrocyclic crowm ether receptors, including molecular design, chemical synthesis and their applications in the fields of supramolecular recognition and sensing. The second part focuses on the synthesis, characterization and recognition properties of three novel ferrocene amide-based thiacalix[4]arene acyclic polyether receptors. Their structures were characterized by IR, P1PH NMR, P13PC NMR, MS and elemental analyses, as well as for one compound being determined by X-ray diffraction techniques. The recognition and sensing properties of these new receptors were investigated by the cyclic voltammetry and UV-Vis titration techniques. Such receptors show selective recognition function towards HB2BPOB4BP-P, FP-Pand EuP3+ Pions.The last part involves the synthesis, and supramolecular recognition properties of three novel thiacalixcrown receptors bearing optical and redox active anthraquinone units. Their structures were fully characterized by IR, P1PH NMR, P13PC NMR, MS, elemental analyses and X-ray diffraction techniques. The recognition and sensing properties of these new receptors were investigated by fluorescence, UV-Vis, and P1PH NMR titrations, theoretical calculations and cyclic voltammetry techniques. It was found that such receptors show a high selectivity towards HB3BOP+P ions.