Complexation of Aliphatic Ammonium Ions with a Water-Soluble Cucurbituril Derivative in Pure Water: Isothermal Calorimetric, NMR, and X-ray Crystallographic Study
Article first published online: 6 MAY 2009
Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chemistry - A European Journal
Volume 15, Issue 25, pages 6143–6151, June 15, 2009
How to Cite
Kim, Y., Kim, H., Ko, Y., Selvapalam, N., Rekharsky, Mikhail V., Inoue, Y. and Kim, K. (2009), Complexation of Aliphatic Ammonium Ions with a Water-Soluble Cucurbituril Derivative in Pure Water: Isothermal Calorimetric, NMR, and X-ray Crystallographic Study. Chem. Eur. J., 15: 6143–6151. doi: 10.1002/chem.200900305
- Issue published online: 5 JUN 2009
- Article first published online: 6 MAY 2009
- Manuscript Received: 4 FEB 2009
- Korean Ministry of Education, Science, and Technology
- Korea Science and Engineering Foundation
- host–guest systems;
- supramolecular chemistry;
Without interference: The complexation of aliphatic ammonium ions with a water-soluble cucurbituril (CB) derivative, CB* (see picture), in pure water is investigated by isothermal titration calorimetry, NMR spectroscopy, and X-ray crystallography. The binding affinity of the host in pure water is 2–5 orders of magnitude higher than that in the presence of interfering ions, such as protons and alkali metal ions.
Complexation of a water-soluble cucurbituril (CB) derivative, cyclohexanocucurbituril (CB*), the cavity dimensions of which are essentially the same as those of CB, with various organic mono- and diammonium ions has been studied by isothermal titration calorimetry and 1H NMR spectroscopy. The binding affinity of CB* with the guest molecules in water is 3–5 and 2–3 orders of magnitude higher than those of CB in 50 % formic acid and in 0.05 m NaCl solution, respectively, which is mainly due to the larger enthalpic gains upon complex formation in the absence of interfering ions, such as protons and Na+. In particular, the binding constant (K) of spermine to CB* was measured to be 3.4×1012 m−1, which is the highest binding constant ever reported for CB or its derivatives. We also obtained the X-ray crystal structures of α,ω-alkanediammonium ions (CnDA2+, n=4–8) and spermine complexes with CB, in which the aliphatic chains of the guest molecules take an extended or partially bent conformation inside the CB cavity, depending on the chain length. The hexamethylene chain of C6DA2+ takes a twisted conformation, which not only allows strong ion–dipole interactions between the ammonium groups and the carbonyl groups at the portals, but also increases hydrophobic interactions between the alkyl part of the guest and the inner wall of the host, which results in the largest enthalpic gain among α,ω-alkanediammonium ions. The thermodynamic parameters associated with the complexation are discussed in relation to the binding modes and conformations of the aliphatic chain of the guest molecules inside the host, which were investigated by 1H NMR spectroscopy and X-ray crystallography.