Orthogonal recognition processes drive the assembly and replication of a [2]rotaxane
Abstract
Within a small, interconnected reaction network, orthogonal recognition processes drive the assembly and replication of a [2]rotaxane. Rotaxane formation is governed by a central, hydrogen-bonding-mediated binding equilibrium between a macrocycle and a linear component, which associate to give a reactive pseudorotaxane. Both the pseudorotaxane and the linear component undergo irreversible, recognition-mediated 1,3-dipolar cycloaddition reactions with a stoppering maleimide group, forming rotaxane and thread, respectively. As a result of these orthogonal recognition-mediated processes, the rotaxane and thread can act as auto-catalytic templates for their own formation and also operate as crosscatalytic templates for each other. However, the interplay between the recognition and reaction processes in this reaction network results in the formation of undesirable pseudorotaxane complexes, causing thread formation to exceed rotaxane formation in the current experimental system. Nevertheless, in the absence of competitive macrocycle-binding sites, realization of a replicating network favoring formation of rotaxane is possible.
Citation
Kosikova , T , Hassan , N I B , Cordes , D B , Slawin , A M Z & Philp , D 2015 , ' Orthogonal recognition processes drive the assembly and replication of a [2]rotaxane ' , Journal of the American Chemical Society , vol. 137 , no. 51 , pp. 16074–16083 . https://doi.org/10.1021/jacs.5b09738
Publication
Journal of the American Chemical Society
Status
Peer reviewed
ISSN
0002-7863Type
Journal article
Description
The financial support for this work was provided by EPSRC (Grant EP/K503162/1 and EP/E017851/1) and the Ministry for Higher Education Malaysia.Collections
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