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National Academy of Sciences, Proceedings of the National Academy of Sciences, 26(106), p. 10438-10443, 2009

DOI: 10.1073/pnas.0809806106

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Encapsulation and Characterization of Proton-Bound Amine Homodimers in a Water Soluble, Self-Assembled Supramolecular Host

Journal article published in 2009 by Dorothea Fiedler, Michael; Fiedler Dorothea; Mugridge Jeffrey; Bergman Robert; Raymond Kenneth Pluth ORCID, Jeffrey S. Mugridge, Robert G. Bergman, Kenneth N. Raymond
This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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Abstract

Cyclic amines can be encapsulated in a water-soluble self-assembled supramolecular host upon protonation. The hydrogen-bonding ability of the cyclic amines, as well as the reduced degrees of rotational freedom, allows for the formation of proton-bound homodimers inside of the assembly that are otherwise not observable in aqueous solution. The generality of homodimer formation was explored with small N -alkyl aziridines, azetidines, pyrrolidines, and piperidines. Proton-bound homodimer formation is observed for N -alkylaziridines ( R = methyl, isopropyl, tert-butyl), N -alkylazetidines ( R = isopropyl, tert-butyl), and N -methylpyrrolidine. At high concentration, formation of a proton-bound homotrimer is observed in the case of N -methylaziridine. The homodimers stay intact inside the assembly over a large concentration range, thereby suggesting cooperative encapsulation. Both G3(MP2)B3 and G3B3 calculations of the proton-bound homodimers were used to investigate the enthalpy of the hydrogen bond in the proton-bound homodimers and suggest that the enthalpic gain upon formation of the proton-bound homodimers may drive guest encapsulation.