SEARCH

SEARCH BY CITATION

Keywords:

  • hydrogen bonds;
  • ionic liquids;
  • kinetic method;
  • mass spectrometry;
  • supramolecular chemistry

Abstract

Electrospray ionization mass spectrometry (ESI-MS) is found to gently and efficiently transfer small to large as well as singly to multiply charged [X+]n[A]m supramolecules of imidazolium ion (X+) ionic liquids to the gas phase, and to reveal “magic numbers” for their most favored assemblies. Tandem mass spectrometric experiments (ESI-MS/MS) were then used to dissociate, via low-energy collision activation, mixed and loosely bonded [A- - - -X- - - -A′] and [X- - - -A- - - -X′]+ gaseous supramolecules, as well as their higher homologues, and to estimate and order via Cooks' kinetic method (CKM) and B3LYP/6-311G(d,p) calculations the intrinsic solvent-free magnitude of hydrogen bonds. For the five anions studied, the relative order of intrinsic hydrogen-bond strengths to the 1-n-butyl-3-methylimidazolium ion [X1]+ is: CF3CO2 (zero) > BF4 (−3.1) > PF6 (−10.0) > InCl4 (−16.4) and BPh4 (−17.6 kcal mol−1). The relative hydrogen-bond strength for InCl4 was measured via CKM whereas those for the other anions were calculated and used as CKM references. A good correlation coefficient (R=0.998) between fragment ion ratios and calculated hydrogen-bond strengths and an effective temperature (Teff) of 430 K demonstrate the CKM reliability for measuring hydrogen-bond strengths in gaseous ionic liquid supramolecules. Using CKM and Teff of 430 K, the intrinsic hydrogen-bond strengths of BF4 for the three cations investigated is: 1-n-butyl-3-methyl-imidazolium ion (0) > 1,3-di-[(R)-3-methyl-2-butyl]-imidazolium ion (−2.4) > 1,3-di-[(R)-α-methylbenzyl]-imidazolium ion (−3.0 kcal mol−1). As evidenced by “magic” numbers, greater stabilities are found for the [(X1)2(BF4)3] and [(X1)5A4]+ supramolecules (A≠InCl4).