Issue 8, 2022

Size-dependent compression of threaded alkyldiphosphate in head to head cyclodextrin [3]pseudorotaxanes

Abstract

The encapsulation of guests in a confined space enables unusual conformations and reactivities. In particular, the compression of akyl chains has been obtained by self-assembled molecular capsules but such an effect has not been reported in solution for pseudorotaxane architectures. By exploiting the tendency of cyclodextrin (CD) to form head to head [3]pseudorotaxanes and the hydrogen bonding abilities of phosphate groups, we have studied the effect of the CD dimer cavity on the conformation of threaded α,ω-alkyl-diphosphate axles. The formation of [2]pseudorotaxanes and [3]pseudorotaxanes was investigated by a combination of NMR, ITC and X-ray diffraction techniques. In the solid state, the [3]pseudorotaxane with a C8 axle presents a fully extended conformation with both terminal phosphate groups interacting with hydroxyl groups of the primary rim of CDs. Such hydrogen bonding interactions are also present with the C9 and C10 axles resulting in a compression of the alkyl chain with gauche conformations in the solid state. NMR studies have shown that this effect is maintained in solution resulting in a size-dependent progressive compression of the alkyl chain by the CD [3]pseudorotaxane architecture for C9, C10 and C11 axles.

Graphical abstract: Size-dependent compression of threaded alkyldiphosphate in head to head cyclodextrin [3]pseudorotaxanes

Supplementary files

Article information

Article type
Edge Article
Submitted
15 oct. 2021
Accepted
16 ene. 2022
First published
17 ene. 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2022,13, 2218-2225

Size-dependent compression of threaded alkyldiphosphate in head to head cyclodextrin [3]pseudorotaxanes

J. Scelle, H. Vervoitte, L. Bouteiller, L. Chamoreau, M. Sollogoub, G. Vives and B. Hasenknopf, Chem. Sci., 2022, 13, 2218 DOI: 10.1039/D1SC05697B

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