Fiche publication
Date publication
avril 2016
Journal
Chemical science
Auteurs
Membres identifiés du Cancéropôle Est :
Dr CHARBONNIERE Loïc
,
Dr ELHABIRI Mourad
Tous les auteurs :
Bilbeisi RA, Prakasam T, Lusi M, El Khoury R, Platas-Iglesias C, Charbonnière LJ, Olsen JC, Elhabiri M, Trabolsi A
Lien Pubmed
Résumé
Two synthetic approaches-temperature variation and anion templation-allowed for the selective formation of a [2]catenane ( ) or a trefoil knot ( ), or for the enhanced formation of a Solomon link ( ), all from a simple set of starting materials (Zn(ii) acetate, diformylpyridine (DFP) and a diamino-2,2'-bipyridine (DAB)) in mixed aqueous solutions. The catenane formed exclusively at 90 °C in a 1 : 1 mixed solvent of DO and MeOD. In the presence of bromide ion as template, formed exclusively at 50 °C in the same solvent. In the solid state, hosts two bromide ions in its central cavity by forming six C -H hydrogen bonds. In DO, , which was originally prepared as a trifluoroacetate (TFA) salt, was found to exchange two TFA counterions for two monovalent anions of different sizes and shapes, which lodged within the knot's central cavity. In contrast to bromide, the larger triflate anion (CFSO) promoted the formation of , which was characterized by H NMR spectroscopy and mass spectrometry. Two dimensional heteronuclear F-H-HOSEY NMR experiments detected CH···F interactions inside the cavity of . Thus, the product distribution of this dynamic link forming system is sensitive to temperature and the size and shape of the anion template, and one of the products, , is capable of binding a variety of monovalent anions in DO with high affinity (with log values of 4 to 6 being typical).
Référence
Chem Sci. 2016 Apr 21;7(4):2524-2531
