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Article Dans Une Revue Journal of the American Chemical Society Année : 2010

Restricted Guest Tumbling in Phosphorylated Self-Assembled Capsules

Résumé

ABii diphosphonatocavitands self-assemble in chloroform solution to form dimeric molecular capsules. The molecular capsules can incarcerate an N-methylpyridinium or N-methylpicolinium guest. We have demonstrated that the supramolecular assembly acts as a molecular rotor as a result of the restricted motion of the guest inside the molecular cavity. In the solid state, X-ray diffraction analysis of the free host showed that two cavitands interact through strong hydrogen bonds to give the supramolecular self-assembled capsule. The solid-state structure of the N-methylpicolinium complex is comparable to that of the free host and indicates that the guest is not a prerequisite for the formation of the capsule. DOSY NMR studies provided a definitive argument for the formation of the free and complexed supramolecular capsule in CDCl3 solution. In solution, the tumbling of the N-methylpyridinium and N-methylpicolinium guests about the equatorial axes of the host can be frozen and differs by the respective energy barriers, with the larger picolinium substrate having a larger value (ΔG⧧ = 69.7 kJ mol−1) than the shorter pyridinium guest (ΔG⧧ = 44.8 kJ mol−1). This behavior corresponds to the restricted rotation of a rotator in a supramolecular rotor.
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hal-01116899 , version 1 (15-02-2015)

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Steven Harthong, Béatrice Dubessy, Jérôme Vachon, Christophe Aronica, Jean-Christophe Mulatier, et al.. Restricted Guest Tumbling in Phosphorylated Self-Assembled Capsules. Journal of the American Chemical Society, 2010, 132 (44), pp.15637-15643. ⟨10.1021/ja104388t⟩. ⟨hal-01116899⟩
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