Abstract
Cation binding by macrocycles was studied using 13C NMR dipole-dipole relaxation measurements in solution. The association constants of [3n]Crown-n and its cyclohexyl, benzo and dioxo derivatives with Li+, Na+, K+ and Ca2+ cations were studied in polar solvents. The relaxation times, T1 obs and NOE factors (η) of 13C atoms in the backbone of free and complex macrocycles were estimated in the extreme narrowing NMR conditions and gave T0 DD and T10 DD dipolar relaxation times. The internal motions coupled with the dipolar relaxation times are influenced by cation binding characterized by the association constants, Ka. The experimental results showed the effect of ionic radii and macrocycle size on ion selectivity as well as on the selectivity between non equivalent binding sites. The energy barriers of the preferential a, ±g,a conformational sequences present in the bound oxyethylene backbone were examined by molecular dynamics simulations using the MM+ force field in commercial software.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
Lisegang, G.W. Eyring, E.M., Synthetic Multidentate Macrocyclic Compounds, Izatt, R.M. and Christensen, J.J., Eds, (1978) Academic, New York, pp-254–260.
Forsen, S., Drakenberg, T. and Wennerström, H. (1987) NMR Studies of Ion Binding in Biological Systems, Quarterly Rewiews of Biophysics, 19(1/2), pp 83–114.
a. Detellier, C. and Laszlo, P. Topics in Molecular Interactions, Thomas, W.J.O-, Ratajczak, H. and Rao, C.N.R. Eds. (1985) Studies in Physical and Theoretical Chemistry, Vol 37, Elsevier, Amsterdam, pp 291–336. b. Hertz, H.G., Kratochwil, A. and Weingärtner, H. Topics in Molecular Interactions, Thomas, W.J.O-., Ratajczak, H. and Rao, C.N.R. Eds (1985) Studies in Physical and Theoretical Chemistry, Vol 37, Elsevier, Amsterdam, pp 337-402.
Grootenhuis, P.D.J., van Eerden, J., Sudhölter, E.J.R., Reinhoudt, D.N., Roos, A., Harkema, S. and Feil, D. (1987) Complexation of Macrocyclic Polyethers Studied by Carbon-13 NMR Relaxation Time Measurements and Molecular Mechanics, J. Amer. Chem. Soc., 109, 4192-4191.
Echegoyen, L, Kaifer, A., Durst, H.D. Gokel, G.W. (1984) Carbon-13 Chemical Shifts and Relaxation Times as a Probe of Structural and Dynamic Properties in Alkali and Alkaline Earth Cryptate Complexes, J. Org. Chem. 49, 688–690.
Srehlow, H. and Knohe, W. (1977) Fundamentals of Chemical Relaxation, VCH, Weinheim, pp 1–98.
a. Erk, Ç. (1986) The 13C Dipole-Dipole Relaxation and Pseudorotation of some Macrocyclic Ethers and a Polyoxa-lactone, Appl. Spectrosc., 41. 100–103, see refs. b. Erk, G. (1989) 13C Dipole-Dipole Relaxation Time and Internal Motions of Oligocyclic Ethers, J. Mol. Liqs., 40, 1-15.
a. Erk, Ç. (1985) Determination of The Association Constants of Macrocyclic Ethers by the Aid of 13C Dipole-Dipole Relaxation Time Measurements. Part I, Spectrosc.Lett., 8(9), 723–750. b. Erk, G. (1986) The Dipole-dipole Relaxation Time and Internal Motions of Cyclic Oligoethers. Part III, Spectrosc.Lett.,19 (10), 1173-1182. c. Erk, G. (1988) The Determination of Macrocyclic Ether Complexes by use of 13C Dipole-Dipole Relaxation Time Measurements. Part. IV, J. Mol. Liqs., 37, 101-115.
a. Erk, Ç. (1988) Host-Guest Interaction Mechanisms with 13C Dipole-Dipole Relaxation Time Measurements. Part V, Equilibrium Constants of Potassium and Sodium Acetates Complexing with 18.crown.6 in CH3OD, J. Mol. Liqs., 40, 143–153. b. Erk, G. (1990) The ion-dipole Interaction Mechanism of Macrocyclic Ethers with 13C Dipole-Dipole Relaxation Time Measurements, Part VI, J. Phys. Chem., 94, 8617-8621 c. Erk, G. (1996) Ion-Dipole Interactions of Macrocyclic Ethers using 13C Dipole-Dipole Relaxation Time Measurements, Part XI, J. Incl.Phen., 26, 61-66 d. Erk, G. and Zeidler, M.D, (1997) 13C NMR Relaxation Time of Benzo[18]crown-6 and Complexing in Acetonitrile with NaClO4,H2O, J. Mol. Liqs., in press.
a. Gakir, Ü and Erk, G. (1991) The Complexation of 18.crown.6 with NaCl in Dioxan-Water and Determination of Equilibrium Constants with ISE, Thermochim.Acta, 178, 61-13. b. GöÁmen, A. and Erk, Ç. (1993) Potentiometric Determination of Stability Constants of Macrocyclic Ethers using Linear Regression Techniques, Fresenius J. Anal. Chem., 347, 471-474. c. GöÁmen, A. and Erk, Ç. (1996) The Cation Binding of Benzo Crowns in Acetonitrile using Fluorescence Spectroscopy, J. Incl. Phen., 26, 67-72.
Anet, F.A.L and Anet, R. (1975) Conformational Process in Rings, Jackman, L.M. & Cotton, F.A., Eds., Dynamic NMR Sspecroscopy, Academic, pp 543–616.
Troxler, L. and Piff, G. (1994) Conformation and Dynamics of 18.Crown.6, Cyriptand 222 and their Cation Complexes in Acetonitrile Studied by Molecular Dynamic Simulations, J. Am. Chem. Soc., 96, 116, 1468.
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1999 Springer Science+Business Media Dordrecht
About this chapter
Cite this chapter
Erk, Ç. (1999). Cation Complexation and Stereochemistry of Macrocycles Studied by 13C NMR Relaxation-Time Measurements. In: Pons, M. (eds) NMR in Supramolecular Chemistry. NATO ASI Series, vol 526. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-4615-9_22
Download citation
DOI: https://doi.org/10.1007/978-94-011-4615-9_22
Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-010-5950-3
Online ISBN: 978-94-011-4615-9
eBook Packages: Springer Book Archive