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NMR Studies of Inclusion Compounds NMR Studies of Inclusion Compounds Sahar Nikkhou Aski Stockholm University © Sahar Nikkhou Aski, Stockholm 2008 ISBN 978-91-7155-715-5 Printed in Sweden by US-AB, Stockholm 2008 Distributor: Department of Physical, Inorganic and Structural Chemistry Stockholm University ii NMR Studies of Inclusion Compounds Sahar Nikkhou Aski Abstract This thesis presents the application of some of the NMR methods in studying host- guest complexes, mainly in solution. The general focus of the work is on investigating the reorientational dynamics of some small molecules that are bound inside cavities of larger moieties. In the current work, these moieties belong to two groups: cryptophanes and cyclodextrins. Depending on the structure of the cavities, properties of the guest molecules and the formed complexes vary. Chloroform and dichloromethane are in slow exchange between the cage-like cavity of the cryptophanes and the solvent, on the chemical shift time scale, whereas adamantanecarboxylic acid, quinuclidine and 1,7-heptanediol in complex with cyclodextrins are examples of fast exchange. Kinetics and thermodynamics of complexation are studied by measuring exchange rates and translational self- diffusion coefficients by means of 1-dimenssional exchange spectroscopy and pulsed-field gradient (PFG) NMR methods, respectively. The association constants, calculated using the above information, give estimates of the thermodynamic stability of the complexes. Carbon-13 spin relaxation data were obtained using conventional relaxation experiments, such as inversion recovery and dynamic NOE, and in some cases HSQC-type (Hetereonuclear Single Quantum Correlation Spectroscopy) experiments. Motional parameters for the free and bound guest, and the host molecules were extracted using different motional models, such as Lipari- Szabo, axially symmetric rigid body, and Clore models. Comparing the overall correlation times and the order parameters of the free and bound guest with the overall correlation time of the host molecule, one can estimate the degree of the motional restriction, brought by the complexation, and the coupling between the motion of the bound guest and the reorientation of the host molecule. In one case, the guest motions were also investigated inside the cavities of a solid host material. iii iv Contents List of papers......................................................................................................vii Preface ................................................................................................................ 1 1- Supramolecular structures............................................................................. 2 1.1 Classification ......................................................................................................2 1.1.1 Complex or clathrate.......................................................................................3 1.1.2 Interactions .....................................................................................................4 1.1.3 Host and guest types ......................................................................................6 1.2 Selectivity..............................................................................................................21 1.3 Application ............................................................................................................22 2- NMR spectroscopy....................................................................................... 24 2.1 - Spin Hamiltonians ...............................................................................................24 2.2 Relaxation - A very brief introduction.....................................................................27 2.2.1 Relaxation mechanisms................................................................................27 2.2.2 Spectral density functions .............................................................................29 2.2.3 Relaxation parameters..................................................................................31 2.2.4 Experimental methods ..................................................................................34 2.3 Chemical exchange..........................................................................................39 2.4 Translational diffusion ...........................................................................................41 3- Dynamics of cyclodextrins and cryptophanes studied by NMR ................ 44 3.1 Stoichiometry and binding constant.......................................................................44 3.2 Nuclear magnetic relaxation..................................................................................46 4- Discussion of the papers ............................................................................. 48 4.1 Papers I-II .............................................................................................................49 4.2 Papers III-V ...........................................................................................................50 Acknowledgment .............................................................................................. 53 References........................................................................................................ 54 v vi List of papers This thesis is based on the following publications and manuscripts. I. Exchange kinetics and 13 C NMR relaxation studies of inclusion complexes of dichloromethane and some cryptophanes S. Nikkhou Aski , A.Y.H. Lo, T. Brotin, J.-P. Dutasta, M. Edén and J. Kowalewski, Journal of Physical Chemistry C, in press Reproduced with kind permission from American Chemical Society ©2008 II. Inclusion complexes of cryptophane–E with dichloromethane and chloroform: A thermodynamic and kinetic study using the 1D- EXSY NMR method S. Nikkhou Aski , Z. Takacs and J. Kowalewski Magnetic Resonance in Chemistry , in press Reproduced with kind permission from John Wiley & Sons Limited ©2008 III. Reorientational dynamics of adamantanecarboxylic acid in complex with β-cyclodextrin Z. Tosner, S. Nikkhou Aski and J. Kowalewski Journal of Inclusion Phenomena and Macrocyclic Chemistry 55 59-70 (2006) Reproduced With kind permission from Science+Bussiness Media IV. Quinuclidine compelx with α-cyclodextrin: a diffusion and 13 C NMR relaxation study. S. Nikkhou Aski and J. Kowalewski Magnetic Resonance in Chemistry 46 261-267, (2008) Reproduced with kind permission from John Wiley & Sons Limited ©2008 V. Interaction between α-cyclodextrin and 1,7-heptanediol. An NMR study of diffusion and carbon-13 relaxation S. Nikkhou Aski , Z. Takacs and J. Kowalewski Manuscript vii The following articles are not included in the thesis. - The effect of pendant-arm modification and ring size on the dynamics of cyclic polyamines J. Wyrwal, G. Schroeder, J. Kowalewski and S. Nikkhou Aski Journal of Molecular Structure 274-279, (2006) - Cross-correlated and conventional dipolar carbon-13 relaxation in methylene groups in small, symmetric molecules L. Ghalebani, P. Bernatowicz, S. Nikkhou Aski and J. Kowalewski Concepts in Magnetic Resonance Part A 30A 100-115, (2007) - Extensive NMRD studies of Ni(II) salt solutions in water and water- grycerol mixtures J. Kowalewski, A. Egorov, D. Kruk, A. Laaksonen, S Nikkhou Aski , G. Parigi and P.-O. Westlund Submitted viii ix Preface The research work described in this dissertation is the result of my PhD study at the division of physical chemistry during the period 2004 - 2008. The thesis is mainly centered on the issue how the motional properties of small molecules change in complexation with somewhat larger moiety named host molecules in liquids. Since the discovery of the naturally occurring supramolecules, there has been an intense interest in studying them. During the past decades, researchers have been doing great amounts of work and investigation in synthetic chemistry to approach the artistic way that nature has designed the functional aggregations of molecules 1. The central approach used in this work is NMR nuclear spin relaxation, in particular, relaxation of the 13 C spin. As complementary tools, it is also taken advantage of some other techniques such as diffusion measurements and kinetic studies using NMR to partly cover the kinetics and thermodynamics of the chemical exchange going on in the systems under study. I would like, however, to emphasize that the most looked forward to aspect of the work was to investigate the effect of complexation on the motion rather than the thermodynamics of inclusion. The main body of the summary is split into two parts: an account of NMR spectroscopy theory and methods, and the systems undergone investigation. The thesis starts with an explanation of inclusion phenomena and the systems chosen to be studied. To maintain briefness, this part is limited mainly to two classes of host molecules. In the following chapter I present the outlines of nuclear magnetic resonance spectroscopy and nuclear spin relaxation. In the same chapter, the experimental approaches employed to obtain the relaxation parameters of the components of the systems is reviewed. In the next part, kinetics and thermodynamics of the complexation and their significance in the applicability of the relaxation study of the system is discussed. There is at last a final conclusion and discussion chapter. This chapter covers the concluding remarks of the papers on which this thesis is set up. 1 1- Supramolecular structures Molecular recognition 2 is the study
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