Binding Selectivity of Macrocycle Ionophores in Ionic Liquids versus Aqueous Solution and Solvent‐free Conditions. Issue 17 (30th September 2015)

• Record Type: Journal Article
• Authors: Gámez, Francisco; Hortal, Ana R.; Hurtado, Paola; Avilés‐Moreno, Juan R.; Hamad, Said; Martínez‐Haya, Bruno
• Is Part Of: Chemphyschem. Volume 16:Issue 17(2015)
• Page Start: 3672
• Page End: 3680
• Publication Date: 2015-09-30
• Subjects: calixarenes -- cyclodextrins -- ionic liquids -- macrocycles -- supramolecular chemistry; Chemistry, Physical and theoretical -- Periodicals; 541.05
• DOI: 10.1002/cphc.201500477
• Languages: English
• ISSNs: 1439-4235

Abstract

Abstract: The understanding of supramolecular recognition in room‐temperature ionic liquids (RTILs) is key to develop the full potential of these materials. In this work, we provide insights into the selectivity of the binding of alkali metal cations by standard cyclodextrin and calixarene macrocycles in RTILs. A direct laser desorption/ionization mass spectrometry approach is employed to determine the relative abundances of the inclusion complexes formed through competitive binding in RTIL solutions. The results are compared with the binding selectivities measured under solvent‐free conditions and in water/methanol solutions. Cyclodextrins and calixarenes in which the peripheral OH groups are substituted by bulkier side groups preferentially bind to Cs + . Such specific ionophoric behavior is substantially enhanced by solvation effects in the RTIL. This finding is rationalized with the aid of quantum mechanical calculations, in terms of the conformational features and steric interactions that drive the solvation of the inclusion complexes by the bulky RTIL counterions. Abstract : Select results : The selectivity of macrocycles (cyclodextrins, calixarenes) with bulky side chains to bind Cs + over other alkali metal cations is enhanced in ionic liquids in comparison to aqueous solutions.