Synthesis And Properties Of Calix[4]arene Based Receptors Containing Transition Metal Clusters

Supramolecular electrochemical recognition is an interesting subject, which focuses on developing novel redox-active receptors. It is very important to both the field of supramolecular chemistry and practical domain of advanced techniques such as ion transport, molecular switch, electrochemical molecular devices and chemical sensors. Tetrahedral transition metal clusters have useful applications in organic synthesis, anticancer drug and materials. Therefore, a study on design, synthesis and supramolecular recognition properties of calix[4]arene based receptors containing redox-activeμ-C2Co2(CO)6 clusters was carried out. The main results are as follows:1. Recent research progress of transition metal-based redox-active calixarene receptors, including molecular design, chemical synthesis as well as their supramolecular electrochemical recognition and sensing properties, was briefly reviewed.2. Four novel calix[4]arene derivatives bearing tetrahedralμ-C2Co2(CO)6 clusters were prepared in good yields, and their electrochemical properties were investigated by cyclic voltammetry.3. The first examples of ferrocene-based calix[4]arene receptors linked by acetylene orμ-C2Co2(CO)6 bridges were synthesized in excellent yields. The recognition and sensing properties of these receptors were studied by cyclic voltammetry, UV-Vis, fluorescence and 1H NMR titrations. It was found that such receptors show a high selectivity towards Cu2+ and H2PO4-.4. A total of seven new calix[4]arene based receptors were synthesized. Their structures were fully characterized by elemental analyses, IR, 1H NMR, 13C NMR and MS spectroscopies, as well as for one calix[4]areneμ-C2Co2(CO)6 cluster compound being determined by X-ray diffraction techniques.