Study on the synthesis and molecular recognition of new receptors for selective complexation of carboxylic acids

• Published in: Tetrahedron 2010-03, Vol.66 (13), p.2486-2491
• Main Authors: Orłowska, Maja, Mroczkiewicz, Michał, Guzow, Katarzyna, Ostaszewski, Ryszard, Kłonkowski, Andrzej M.
• Format: Article
• Language: English
• Subjects: Anion receptors; Chemistry; Condensed benzenic and aromatic compounds; Coordination compounds; Exact sciences and technology; Inorganic chemistry and origins of life; Organic chemistry; Preparations and properties; Pyrene; Thiouronium salts
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2010.01.066

A new synthetic method based on the synthesis of unsymmetrical thioureas followed by double S-alkylation reaction by xylylene dibromides was used to obtain isothiouronium receptors. Their binding abilities to acetate, succinate and maleate anions were evaluated by UV–vis spectroscopic titrations in such solvents as water, acetonitrile, methanol and mixtures of acetonitrile/methanol (1:1, v/v). For simple receptor 4 with one isothiouronium group, no selectivity was observed in the complexation of the anions studied. Receptors (R) 5a–c with two thiouronium groups are able to form with all the anions studied (A) not only stable complexes of 1:1 stoichiometry but also other possessing structure of the type AnRm. The most reliable values of stability constants are for systems of the type maleate anion-receptor 5 and acetate-receptor 5b. However, the best selectivity in the mixed solvents is demonstrated by anion-5c system. The study indicates also that particularly 5c is preferred as a chemosensor for the maleate anion. The obtained results suggest that subtle changes in the receptor structure lead to different binding modes towards anions. [Display omitted]