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 cross-catalytic 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.
| Original language | English |
|---|---|
| Pages (from-to) | 16074-16083 |
| Number of pages | 10 |
| Journal | Journal of the American Chemical Society |
| Volume | 137 |
| Issue number | 51 |
| DOIs | |
| Publication status | Published - 30 Dec 2015 |
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ASJC Scopus subject areas
- Chemistry(all)
- Catalysis
- Biochemistry
- Colloid and Surface Chemistry
Cite this
Orthogonal Recognition Processes Drive the Assembly and Replication of a [2]Rotaxane. / Kosikova, Tamara; Hassan, Nurul Izzaty; Cordes, David B.; Slawin, Alexandra M Z; Philp, Douglas.
In: Journal of the American Chemical Society, Vol. 137, No. 51, 30.12.2015, p. 16074-16083.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Orthogonal Recognition Processes Drive the Assembly and Replication of a [2]Rotaxane
AU - Kosikova, Tamara
AU - Hassan, Nurul Izzaty
AU - Cordes, David B.
AU - Slawin, Alexandra M Z
AU - Philp, Douglas
PY - 2015/12/30
Y1 - 2015/12/30
N2 - 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 cross-catalytic 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.
AB - 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 cross-catalytic 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.
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U2 - 10.1021/jacs.5b09738
DO - 10.1021/jacs.5b09738
M3 - Article
AN - SCOPUS:84953432987
VL - 137
SP - 16074
EP - 16083
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 51
ER -