Positive Cooperative Effect in Ion‐Pair Recognition by a Tris‐urea Hemicryptophane Cage

• Published in: Chemistry : a European journal Vol. 25; no. 13; pp. 3337 - 3342
• Main Authors: Delecluse, Magalie, Colomban, Cédric, Moraleda, Delphine, de Riggi, Innocenzo, Duprat, Françoise, Michaud‐Chevallier, Sabine, Dutasta, Jean‐Pierre, Robert, Vincent, Chatelet, Bastien, Martinez, Alexandre
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 01.03.2019; Wiley Subscription Services, Inc; Wiley-VCH Verlag
• Subjects: Anions; Cages; Chemical Sciences; Chemical synthesis; Chemistry; Chemistry, Multidisciplinary; cooperativity; density functional calculations; hemicryptophane; host–guest chemistry; Ion pairs; ion-pair recognition; Physical Sciences; Science & Technology; Urea; Ureas; density functional calculations; EXTRACTION; ion-pair recognition; PHOSPHONATE; cooperativity; hemicryptophane; MOLECULAR RECOGNITION; ANION TRANSPORT; host-guest chemistry; RECEPTORS; BINDING; COMPLEXATION; hemicryptophane ion-pair recognition cooperativity Host-guest chemistry DFT calculations
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201805534

The synthesis of a hemicryptophane cage combining a CTV unit with a C3 symmetrical moiety bearing three urea functions is reported. This host was found to bind anions with higher binding constants than other previously reported hemicryptophanes. Due to its heteroditopic character this cage proved to be an efficient ion‐pair receptor. The best cooperativity effect was observed for the tetramethylammonium bromide (TMABr) salt, which was confirmed and rationalized by DFT calculations. A tris‐urea unit was combined with CTV moiety, leading to a heteroditopic hemicryptophane capable of binding ion pairs efficiently and selectively.