Evaluating the energy landscape of an out-of-equilibrium bistable [2]rotaxane containing monopyrrolotetrathiafulvalene

Neumann, Mathias S.; Smith, Amanda F.; Jensen, Sofie K.; Frederiksen, Rikke; Skavenborg, Mathias Lander  Lander; Jeppesen, Jan O.

doi:10.1039/d3cc00360d

Cited by 4 publications

(2 citation statements)

References 33 publications

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“…2 b ,3,4,5 Large amplitude motion in AMMs, similar to what can be observed in biomachines, can be achieved by conformational or configurational changes in covalently bonded molecules 5 g ,6 or in supramolecular architectures. 5 h ,7 In both cases, control of directionality is of paramount importance if rectified motion, such as unidirectional linear motion or unidirectional circumrotational motion in AMMs should be realised. In the latter case, significant progress toward this end has been made possible as a consequence of the formation/discovery of the mechanical bond.…”

Section: Introductionmentioning

confidence: 99%

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Mechanistic studies of isomeric [2]rotaxanes consisting of two different tetrathiafulvalene units reveal that the movement of cyclobis(paraquat-p-phenylene) can be controlled

Jensen,

Neumann,

Frederiksen

et al. 2023

Chem. Sci.

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Section: Introductionmentioning

confidence: 99%

“…‡ ‡ The combination of an SMe and an SR group constitutes a larger barrier for the CBPQT 4+ ring than the pyrrole moiety which results in CBPQT 4+ initially moving across the pyrrole moiety upon oxidation of the MPTTF unit. 7 e …”

Section: Introductionmentioning

confidence: 99%

Mechanistic studies of isomeric [2]rotaxanes consisting of two different tetrathiafulvalene units reveal that the movement of cyclobis(paraquat-p-phenylene) can be controlled

Jensen,

Neumann,

Frederiksen

et al. 2023

Chem. Sci.

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Synthesis of ‘Impossible’ Rotaxanes

Saura‐Sanmartin

2024

Chemistry A European J

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'Impossible' rotaxanes, which are constituted by interlocked components without obvious binding motifs, have attracted the interest of the mechanically interlocked molecules (MIMs) community. Within the synthetic efforts reported in the last decades towards the preparation of MIMs, some innovative protocols for accessing 'impossible' rotaxanes have been developed. This short review highlights different selected synthetic examples of 'impossible' rotaxanes, as well as suggests some future directions of this research area.

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Insight from Electrochemical Analysis in the Radical Cation State of a Monopyrrolotetrathiafulvalene‐Based [2]Rotaxane

Neumann,

Flood,

Jeppesen

2024

Chemistry A European J

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Mechanically interlocked molecules are a class of compounds used for controlling directional movement when barriers can be raised and lowered using external stimuli. Applied voltages can turn on redox states to alter electrostatic barriers but their use for directing motion requires knowledge of their impact on the kinetics. Herein, we make the first measurements on the movement of cyclobis(paraquat‐p‐phenylene) (CBPQT4+) across the radical‐cation state of monopyrrolotetrathiafulvalene (MPTTF) in a [2]rotaxane using variable scan‐rate electrochemistry. The [2]rotaxane is designed in a way that directs CBPQT4+ to a high‐energy co‐conformation upon oxidation of MPTTF to either the radical cation (MPTTF•+) or the dication (MPTTF2+). 1H NMR spectroscopic investigations carried out in acetonitrile at 298 K showed direct interconversion to the thermodynamically more stable ground‐state co‐conformation with CBPQT4+ moving across the oxidized MPTTF2+ electrostatic barrier. The electrochemical studies revealed that interconversion takes place by movement of CBPQT4+ across both the MPTTF•+ (19.3 kcal mol−1) and MPTTF2+ (18.7 kcal mol−1) barriers. The outcome of our studies shows that MPTTF has three accessible redox states that can be used to kinetically control the movement of the ring component in mechanically interlocked molecules.

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Evaluating the energy landscape of an out-of-equilibrium bistable [2]rotaxane containing monopyrrolotetrathiafulvalene

Abstract: The unique redox properties of monopyrrolotetrathiafulvalene can be used to induce directional movement in interlocked molecules. In this study, the kinetics for the directional movement of cyclobis(paraquat-p-phenylene) across the dioxidised...

Cited by 4 publications

References 33 publications

Mechanistic studies of isomeric [2]rotaxanes consisting of two different tetrathiafulvalene units reveal that the movement of cyclobis(paraquat-p-phenylene) can be controlled

Mechanistic studies of isomeric [2]rotaxanes consisting of two different tetrathiafulvalene units reveal that the movement of cyclobis(paraquat-p-phenylene) can be controlled

Synthesis of ‘Impossible’ Rotaxanes

Insight from Electrochemical Analysis in the Radical Cation State of a Monopyrrolotetrathiafulvalene‐Based [2]Rotaxane

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