Sulfur-containing amide-based rotaxanes and molecular shuttles
Altieri, Andrea, Aucagne, Vincent, Carrillo, Romen, Clarkson, Guy J., D'Souza, Daniel M., Dunnett, Jennifer A., Leigh, David A. and Mullen, Kathleen M.. (2011) Sulfur-containing amide-based rotaxanes and molecular shuttles. Chemical Science, Vol.2 (No.10). pp. 1922-1928. ISSN 2041-6520Full text not available from this repository.
Official URL: http://dx.doi.org/10.1039/c1sc00335f
We report on the synthesis, structure and properties of 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 center dot center dot center dot O=SO and NH center dot center dot center dot 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.
|Item Type:||Journal Article|
|Subjects:||Q Science > QD Chemistry|
|Divisions:||Faculty of Science > Chemistry|
|Library of Congress Subject Headings (LCSH):||Sulfur, Rotaxanes, Amides, Macrocyclic compounds, Hydrogen bonding|
|Journal or Publication Title:||Chemical Science|
|Publisher:||Royal Society of Chemistry|
|Page Range:||pp. 1922-1928|
|Access rights to Published version:||Restricted or Subscription Access|
|Funder:||European Research Council (ERC), Engineering and Physical Sciences Research Council (EPSRC), Deutsche Akademie der Naturforscher Leopoldina (DANL), Peter und Traudl Engelhorn-Stiftung (PTES), Fundación Ramón Areces (FRA)|
|Grant number:||LPD 9901/8-166 (DANL)|
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