Rotaxane Catalysts

Leigh, David A.; Marcos, Vanesa; Wilson, Miriam R.

doi:10.1021/cs5013415

Cited by 178 publications

(86 citation statements)

References 108 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For example, the three dimensional structures of certain catenanes and rotaxanes have been used to achieve selectivity in the binding and sensing of ionic and small molecular guest species . Meanwhile, others have been shown to act as catalysts, including examples for which controlled motion of the interlocked components is used to switch catalytic activity on and off . Examples of chiral catenanes and rotaxanes being used in such applications have been somewhat rare, but are now growing in number.…”

Section: Chiral Catenanes and Rotaxanes In Applicationmentioning

confidence: 99%

“…[15] Meanwhile, others have been shown to act as catalysts, including examples for whichc ontrolled motiono ft he interlocked components is used to switchc atalytic activity on and off. [16] Examples of chiral catenanes and rotaxanes being used in such applicationsh ave been somewhat rare, but are now growing in number.…”

Section: Chiral Catenanes and Rotaxanes In Applicationmentioning

confidence: 99%

See 1 more Smart Citation

Chiral Catenanes and Rotaxanes: Fundamentals and Emerging Applications

Evans

2017

Chemistry A European J

View full text Add to dashboard Cite

Molecular chirality provides a key challenge in host–guest recognition and other related chemical applications such as asymmetric catalysis. For a molecule to act as an efficient enantioselective receptor, it requires multi‐point interactions between host and chiral guest, which may be achieved by an appropriate chiral 3D scaffold. As a consequence of their interlocked structure, catenanes and rotaxanes may present such a 3D scaffold, and can be chiral by inclusion of a classical chiral element and/or as a consequence of the mechanical bond. This Minireview presents illustrative examples of chiral [2]catenanes and [2]rotaxanes, and discusses where these molecules have been used in chemical applications such as chiral host–guest recognition and asymmetric catalysis.

show abstract

Section: Chiral Catenanes and Rotaxanes In Applicationmentioning

confidence: 99%

Section: Chiral Catenanes and Rotaxanes In Applicationmentioning

confidence: 99%

Chiral Catenanes and Rotaxanes: Fundamentals and Emerging Applications

Evans

2017

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Such molecules are most well known for their potential to act as components of molecular machines due to the possibility of large amplitude motion of their interlocked components. [3] Furthermore, a range of useful functions of interlocked molecules have been demonstrated, [4] including their use in catalysis [5] and as hosts for ionic and molecular guests. [6] The vast majority of such molecules have been and are still prepared by template synthesis.…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in the Synthesis and Application of Hydrogen Bond Templated Rotaxanes and Catenanes

Evans

2019

Eur J Org Chem

View full text Add to dashboard Cite

Alongside the use of metal cations and π–π stacking, hydrogen bonding is one of the major templating interactions used to prepare rotaxanes and catenanes. In this review, a brief summary of key historical milestones will be followed by discussion of developments from over the last decade in both synthetic methodology and application of hydrogen bond templated interlocked molecules. Hydrogen bond templation can allow for rapid access to interlocked molecules in high yields, with select examples having been put to useful purpose, in applications such as organocatalysis and cellular imaging.

show abstract

“…Supramolecular chemists, who often claim to be inspired by natural systems have, however, dedicated much more efforts to control molecular organization in space than in time. [7][8][9][10][11][12][13] Most of these applications are proposed on the basis of bistable rotaxanes (or pseudorotaxanes) and on their switching ability upon the application of a given stimulus. [2][3][4][5][6] Rotaxanes, for instance, are typically assembled from a macrocycle (wheel) threaded onto one linear molecule (axle) bearing bulky substituents (stoppers) that prevent disassembly.…”

Section: Introductionmentioning

confidence: 99%

Spatiotemporal control over the co-conformational switching in pH-responsive flavylium-based multistate pseudorotaxanes

et al. 2015

View full text Add to dashboard Cite

A multistate molecular dyad containing flavylium and viologen units was synthesized and the pH dependent thermodynamics of the network completely characterized by a variety of spectroscopic techniques such as NMR, UV-vis and stopped-flow. The flavylium cation is only stable at acidic pH values. Above pH ≈ 5 the hydration of the flavylium leads to the formation of the hemiketal followed by ring-opening tautomerization to give the cis-chalcone. Finally, this last species isomerizes to give the trans-chalcone. For the present system only the flavylium cation and the trans-chalcone species could be detected as being thermodynamically stable. The hemiketal and the cis-chalcone are kinetic intermediates with negligible concentrations at the equilibrium. All stable species of the network were found to form 1 : 1 and 2 : 1 host : guest complexes with cucurbit[7]uril (CB7) with association constants in the ranges 10(5)-10(8) M(-1) and 10(3)-10(4) M(-1), respectively. The 1 : 1 complexes were particularly interesting to devise pH responsive bistable pseudorotaxanes: at basic pH values (≈12) the flavylium cation interconverts into the deprotonated trans-chalcone in a few minutes and under these conditions the CB7 wheel was found to be located around the viologen unit. A decrease in pH to values around 1 regenerates the flavylium cation in seconds and the macrocycle is translocated to the middle of the axle. On the other hand, if the pH is decreased to 6, the deprotonated trans-chalcone is neutralized to give a metastable species that evolves to the thermodynamically stable flavylium cation in ca. 20 hours. By taking advantage of the pH-dependent kinetics of the trans-chalcone/flavylium interconversion, spatiotemporal control of the molecular organization in pseudorotaxane systems can be achieved.

show abstract

Rotaxane Catalysts

Cited by 178 publications

References 108 publications

Chiral Catenanes and Rotaxanes: Fundamentals and Emerging Applications

Chiral Catenanes and Rotaxanes: Fundamentals and Emerging Applications

Recent Advances in the Synthesis and Application of Hydrogen Bond Templated Rotaxanes and Catenanes

Spatiotemporal control over the co-conformational switching in pH-responsive flavylium-based multistate pseudorotaxanes

Contact Info

Product

Resources

About