Studies On Synthesis, Characterization And Supramolecular Electrochemical Recognition Of Ferrocene-Based Multisite Receptors

In view of the redox-active organometallic receptors being great important toboth theoretical field of supramolecular chemistry and practical field of advancedtechniques of ion transport and molecular switch, a study on design, synthesis andfunctions of open-chain multiple recognition sites receptors with ferrocene asredox-active center was systematically carried out. The main results are as follows:1. A total of 14 novel ferrocene-based acyclic multi-site receptors weresuccessfully synthesized. The structures for all these new compounds were fullycharacterized by elemental analysis, IR, ¹H NMR, ¹³C NMR and MS, as well as for 2open-chain crown ethers with ferrocene moiety being determined by X-ray diffractiontechniques.2. First ferrocene-based acyclic multi-site receptors containing thiourea functiongroups were synthesized by the classical esterification, reduction, addition reactions.The electrochemical sensing properties of these receptors were measured by cyclicvoltammetry technique and shown selective recognition function towards Mg²⁺ andH₂PO₄^2-.3. Novel ferrocene amide-based acyclic crown ether receptors were prepared viathe selective acylation reaction. The recognition studies show that these new receptorshave good electrochemical sensing properties towards H₂PO₄^2- anion.4. The first examples of ferrocene urea-based acyclic crown ether receptors weresynthesized. It was found that such receptors show a high selectivity towards H₂PO₄^-,CH₃COO^-anions. In addition, the polyether chains exhibit an electrochemicalresponse to K⁺ detected by ¹H NMR titration and cyclic voltammetry technique. Thusit is of great importance to develop the novel ion-pair electrochemical sensors.