Studies On Synthesis, Characterization And Recognition Properties Of Novel Calixcrown Receptors Containing Ferrocene Unit

Supramolecular electrochemical recognition is an emerging and interestingsubject, which focuses on developing novel redox-active receptors. It is greatlyimportant to both the field of supramolecular chemistry and practical domain ofadvanced techniques of ion transport, molecular switch, electrochemical moleculardevices and chemical sensors. Therefore, a study on design, synthesis andsupramolecular properties of calixcrown macrocyclic di-topic receptors withferrocene as redox-active center was systematically carried out. The main results areas follows:1. Recent research progress of redox-active calixarene receptors, includingmolecular design, chemical synthesis and their supramolecular electrochemicalrecognition and sensing properties, was briefly reviewed.2. A total of 12 novel acyclic and macrocyclic calixcrown receptors weresuccessfully synthesized. The structures for all these receptors were fullycharacterized by elemental analysis, IR, ¹H NMR, ¹³C NMR and MS spectroscopies,as well as for two compounds being determined by x-ray diffraction techniques.3. Three novel ferrocene-based calixcrown macrocyclic receptors containing acylthiourea groups were successfully prepared via the selective O-dialkylation, catalyticreduction and addition reactions.4. The first examples of ferrocene amide-based calixcrown di-topic receptors, inwhich the amide groups and calixcrown moiety are designed as anion and cationbinding sites respectively, were synthesized in good yields.5. The recognition and sensing properties of these new receptors wereinvestigated by the cyclic voltammetry and ¹H NMR tritration techniques. It wasfound that these redox-active receptors show a high selectivity towards H₂PO₄-andAg⁺.