Successive Translocation of the Rings in a [3]Rotaxane

Jagesar, Dhiredj C.; Wiering, P. G.; Kay, Euan R.; Leigh, David A.; Brouwer, Albert M.

doi:10.1002/cphc.201501162

Cited by 10 publications

(4 citation statements)

References 61 publications

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“…Considering that these submolecular movements are correlated to the intramolecular interactions, a complete study of these interactions is necessary. The large family of rotaxanes that is based on a thread containing a hydrogen-bonding template for the benzylic amide macrocycle has the shuttling and pirouetting movements well-established in solution, − but only once have these rotaxanes been studied in the solid state . These compounds have rarely been investigated in the literature within static quantum chemical calculations. , …”

Section: Introductionmentioning

confidence: 99%

Density Functional Theory and Quantum Theory of Atoms in Molecules Analysis: Influence of Intramolecular Interactions on Pirouetting Movement in Tetraalkylsuccinamide[2]rotaxanes

Martins

Rodrigues

Meyer

et al. 2017

Crystal Growth & Design

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The first Quantum Theory of Atoms in Molecules (QTAIM) analysis of [2]rotaxanes was used in combination with quantum mechanical calculations and variable temperature NMR experiments. The study shows all the intramolecular interactions of tetraalkylsuccinamide[2]rotaxanes with different templates. The threads have different stoppers [R1R2NC(O)-CH2CH2-C(O)NR2R1, in which R2/R1 = CH2 cy-Hex/CH2Ph, i-Bu, Bu, and Pr]. The different threads used allowed us verify that the contact area between the submolecular components (C Mcy···Thr) is closely correlated with the interaction energy (G Mcy···Thr) in the [2]rotaxanes studied. Furthermore, the QTAIM data and quantum mechanical calculations confirmed that, in all of the compounds, the hydrogen bonds are responsible for most of the energy from the intramolecular interactions that follow the C–H···π and H···H interactions, independent of the thread used. In the liquid state, using NMR 1H some intramolecular interactions were observed, which is in agreement with the data obtained in the solid state, thus making possible a comparison between the energy data obtained via the quantum mechanical calculations and the molecular movements of the [2]rotaxanes in solution. Consequently, a new way of understanding the intramolecular interactions in [2]rotaxanes and the influence they have on the movement of molecular machines is presented.

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Section: Introductionmentioning

confidence: 99%

Density Functional Theory and Quantum Theory of Atoms in Molecules Analysis: Influence of Intramolecular Interactions on Pirouetting Movement in Tetraalkylsuccinamide[2]rotaxanes

Martins

Rodrigues

Meyer

et al. 2017

Crystal Growth & Design

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“…The molecular topologies and architectures associated with mechanical bonds dictate the nature of the relative motions of their components. For example, rotaxanes and catenanes, the archetypal MIMs, exhibit motions such as translocation, − circumrotation, pirouetting, and rocking . These motions are key elements when it comes to the design and operation of molecular machines , such as switches, , rotors, − motors, and pumps. − …”

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confidence: 99%

Suit[4]ane

Liu

Stern

2020

J. Am. Chem. Soc.

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Suitanes are two-component mechanically interlocked molecules in which one (torso) of the components, with several protruding limbs, is encompassed by another (suit) all-in-one component. This kind of molecular ship-in-a-bottle architecture remains a challenging one to make. Herein, we report a porphyrin-based suit[4]ane, which is composed of a porphyrin with four protruding ligands (two phenyl groups and two bromine atoms) called the limbs that are encompassed by a tricyclic octacationic cyclophane. The suit[4]ane can be obtained by slippage, a mechanism by which the cyclophane is able to open up two of its entrances in order to take up the porphyrin at high temperature and close them down at low temperature, locking the porphyrin inside its binding cavity. Dynamic 1H NMR spectroscopy reveals that the trapped porphyrin inside the cyclophane rocks back and forth in the suit[4]ane about 1000 times a second.

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“…Molecular machines and switches with three components are well represented by [3]pseudorotaxanes (9)(10)(11)(12)(13)(14), [3]catenanes (15)(16)(17)(18), and [3]rotaxanes (19)(20)(21)(22)(23)(24)(25). Examples include unidirectional motion of two small rings around a larger ring (15) and muscle-like contraction of two rings along a dumbbell in a [3] rotaxane (20).…”

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confidence: 99%

Inchworm movement of two rings switching onto a thread by biased Brownian diffusion represent a three-body problem

Benson

Fatila

Liu

et al. 2018

Proc. Natl. Acad. Sci. U.S.A.

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The coordinated motion of many individual components underpins the operation of all machines. However, despite generations of experience in engineering, understanding the motion of three or more coupled components remains a challenge, known since the time of Newton as the "three-body problem." Here, we describe, quantify, and simulate a molecular three-body problem of threading two molecular rings onto a linear molecular thread. Specifically, we use voltage-triggered reduction of a tetrazine-based thread to capture two cyanostar macrocycles and form a [3]pseudorotaxane product. As a consequence of the noncovalent coupling between the cyanostar rings, we find the threading occurs by an unexpected and rare inchworm-like motion where one ring follows the other. The mechanism was derived from controls, analysis of cyclic voltammetry (CV) traces, and Brownian dynamics simulations. CVs from two noncovalently interacting rings match that of two covalently linked rings designed to thread via the inchworm pathway, and they deviate considerably from the CV of a macrocycle designed to thread via a stepwise pathway. Time-dependent electrochemistry provides estimates of rate constants for threading. Experimentally derived parameters (energy wells, barriers, diffusion coefficients) helped determine likely pathways of motion with rate-kinetics and Brownian dynamics simulations. Simulations verified intercomponent coupling could be separated into ring-thread interactions for kinetics, and ring-ring interactions for thermodynamics to reduce the three-body problem to a two-body one. Our findings provide a basis for high-throughput design of molecular machinery with multiple components undergoing coupled motion.

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Successive Translocation of the Rings in a [3]Rotaxane

Cited by 10 publications

References 61 publications

Density Functional Theory and Quantum Theory of Atoms in Molecules Analysis: Influence of Intramolecular Interactions on Pirouetting Movement in Tetraalkylsuccinamide[2]rotaxanes

Density Functional Theory and Quantum Theory of Atoms in Molecules Analysis: Influence of Intramolecular Interactions on Pirouetting Movement in Tetraalkylsuccinamide[2]rotaxanes

Suit[4]ane

Inchworm movement of two rings switching onto a thread by biased Brownian diffusion represent a three-body problem

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