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The Synergetic Interplay of Weak Interactions in the Ion‐Pair Recognition of Quaternary and Diquaternary Ammonium Salts by Halogenated Resorcinarenes
Author(s) -
Kodiah Beyeh N.,
Göth Melanie,
Kaufmann Lena,
Schalley Christoph A.,
Rissanen Kari
Publication year - 2014
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201300886
Subject(s) - chemistry , fourier transform ion cyclotron resonance , halogen bond , hydrogen bond , halogen , ammonium , inorganic chemistry , electrospray ionization , non covalent interactions , electronegativity , ion cyclotron resonance , ionic bonding , iodide , titration , computational chemistry , ion , organic chemistry , molecule , alkyl , cyclotron
The influence of halogens on the noncovalent interactions of different upper‐rim‐substituted hexylresorcinarenes with quaternary and diquaternary ammonium iodide salts was investigated in the gas phase by electrospray ionization Fourier‐transform ion‐cyclotron‐resonance (ESI‐FTICR) mass spectrometry and in solution by 1 H NMR titration studies. The electronic nature of the substituents on the upper rim of the resorcinarene was directly reflected in the order of binding strengths of the hosts towards quaternary and diquaternary ammonium cations in the gas phase. In solution, the opposite trend was observed, with generally higher binding constants for the diquaternary over the quaternary salts. This phenomenon is explained by the synergetic effect originating from the interaction of the halogenated resorcinarenes with the counteranions through enhanced hydrogen bonding, leading to ion‐pair binding in solution. The electronegativity of the halogens renders the hydrogen of the hydroxy group more acidic, and hence enforces hydrogen bonding in solution. The collective effect of several weak interactions is manifested in solution, thereby emphasizing the benefits of comparing solution and gas‐phase studies in recognition processes.