Sulfur-containing amide-based [2]rotaxanes and molecular shuttles

Altieri, Andrea, Aucagne, Vincent, Carrillo, Romen, Clarkson, Guy J., D'Souza, Daniel M., Dunnett, Jennifer A., Leigh, David A., & Mullen, Kathleen M. (2011) Sulfur-containing amide-based [2]rotaxanes and molecular shuttles. Chemical Science, 2(10), pp. 1922-1928.

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We report the synthesis, structure and properties of [2]rotaxanes prepared by the assembly of benzylic amide macrocycles around a series of amide and sulfide-/sulfoxide-/sulfone-containing threads. The efficacy of rotaxane formation is related to the hydrogen bond accepting properties of the various sulfur-containing functional groups in the thread, with the highest yields (up to 63% with a rigid vinyl spacer in the template site) obtained for sulfoxide rotaxanes. X-Ray crystallography of a sulfoxide rotaxane, 5, shows that the macrocycle adopts a highly symmetrical chair-like conformation in the solid state, with short hydrogen bonds between the macrocycle isophthalamide NH-protons and the amide carbonyl and sulfoxide S-O of the thread. In contrast, in the X-ray crystal structures of the analogous sulfide (4) and sulfone (6) rotaxanes the macrocycle adopts boat-like conformations with long intercomponent NH…O=SO and NH…S hydrogen bonds (in addition to several intercomponent amide-amide hydrogen bonds). Taking advantage of the different hydrogen bonding modes of the sulfur-based functional groups, a switchable molecular shuttle was prepared in which the oxidation level of sulfur determines the position of the macrocycle on the thread.

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ID Code: 72049
Item Type: Journal Article
Refereed: Yes
DOI: 10.1039/C1SC00335F
ISSN: 2041-6539
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Copyright Owner: Copyright 2011 Royal Society of Chemistry
Deposited On: 25 May 2014 23:08
Last Modified: 01 Jun 2014 04:07

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