Optical reading of the open and closed states of a molecular turnstile

Zigon, Nicolas; Larpent, Patrick; Jouaiti, Abdelaziz; Kyritsakas, Nathalie; Hosseini, Mir Wais

doi:10.1039/c4cc01071j

Cited by 21 publications

(15 citation statements)

References 26 publications

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“…Still, we felt that theoretical inspection might be desirable to support the mechanistic views and to rationalize the actual molecular rotation. In the meantime, Hosseini and co‐workers reported on molecular turnstiles, constructed on a rotor (typically a tetraethylene glycol (TEG) chain grafted onto a porphyrin, an organometallic or an aromatic moiety) and a stator . With the possibility to introduce a photo‐sensitive group almost at will on the stator, we designed a system where the macrocycle structure would be maintained upon irradiation.…”

Section: Methodsmentioning

confidence: 99%

“…The design of the AzoT macrocycle (Scheme ) stems from the molecular turnstiles previously reported, to which a pyridyl moiety was introduced to better follow its dynamical behavior by 1 H NMR spectroscopy. On the other side the light‐responsive Azo moiety can be isomerized between E (thermodynamically stable) and Z (metastable) using different excitation wavelengths, with concomitant large geometrical change of the compound.…”

Section: Methodsmentioning

confidence: 99%

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The Motion of an Azobenzene Light‐Controlled Switch: A Joint Theoretical and Experimental Approach

et al. 2019

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To gain further insight into the internal motion of molecular objects, we have synthesized a molecular turnstile AzoT composed of a rotor based on flexible tetraethyleneglycol (TEG) chains grafted on aromatic moieties and a stator containing a photoswitchable azobenzene (Azo) fragment. The control of the reversible light‐induced E‐AzoT⇆Z‐AzoT isomerization is supported by both NMR spectroscopy and photophysical investigation, which show that the system exhibits a fatigueless isomerization switching process. Furthermore, 2D NMR spectroscopy points to the fact that the free internal motion is triggered by the E‐AzoT⇆Z‐AzoT isomerization. Using molecular dynamics simulations and DFT calculations we have investigated the nature of the internal motions. An internal rotation characterized by an energy barrier of 23 kJ/mol is found for the Z‐AzoT isomer. In contrast, this barrier reaches 151 kJ/mol for the E‐AzoT isomer, excluding any “classical” rotation at room temperature. This rotational movement could in principle occur via tunneling. A simple model calculation, however, excludes tunnelling to take place before 20 ms.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

The Motion of an Azobenzene Light‐Controlled Switch: A Joint Theoretical and Experimental Approach

et al. 2019

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“…Along with this transformation the originally non‐fluorescent copper(I) rectangle was transformed into the luminescent ladder [Zn 4 ( 29 ) 2 ( 30 ) 2 ] 8+ . Other examples include redox‐triggered cargo shipping and switching, as well as Hosseini's turnstiles ,…”

Section: Multiple Self‐sorting Events: From Structural Reorganizationmentioning

confidence: 99%

Dynamic Functional Molecular Systems: From Supramolecular Structures to Multi‐Component Machinery and to Molecular Cybernetics

Schmittel

2018

Israel Journal of Chemistry

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This essay highlights the role of single and multiple reversible self‐sorting events for the development of responsive multi‐component structures as well as multi‐state transformations, devices and machinery. Recent examples illustrate how distinct molecular devices are spatiotemporarily interconnected by chemical signaling to act as integrated machinery and highlight the enormous potential of molecular cybernetics.

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“…[30][31][32] Recently, we have described a purely organic turnstile with optical reading between its open and closed states. 33 Continuing our efforts in this area, herein, we report on another molecular turnstile 1 (Scheme 1) for which the open and closed states may be differentiated by their emission property.…”

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confidence: 99%

“…1, C). Based on our previous investigation on an analogous system, 33 whereas the open state of the turnstile should luminesce, its closed state, owing to the heavy atom effect of Pd(II), should be far less emissive.…”

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confidence: 99%

A luminescent molecular turnstile

et al. 2014

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A molecular turnstile based on a hydroquinone luminescent hinge bearing two divergently oriented pyridyl units behaving as a rotor and equipped with a handle composed of a tridentate coordinating site considered as the stator was synthesized and its structure was studied in the solid state by X-ray diffraction on single crystal. Its dynamic behaviour in solution was investigated by 1- and 2-D NMR experiments which revealed the free rotation of the rotor around the stator. The rotational movement was locked upon addition of Pd(ii) simultaneously complexed by the tridentate moiety of the stator and one of the two monodentate pyridyl sites of the rotor. Interestingly, whereas the open state of the turnstile was luminescent, for its closed state the emission was quenched by the heavy atom effect of Pd(ii).

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Optical reading of the open and closed states of a molecular turnstile

Abstract: A molecular turnstile composed of a hydroquinone based rotor and a stator bearing a tridentate coordinating site can be reversibly switched between open and closed states. The locking and unlocking processes may be read optically.

Cited by 21 publications

References 26 publications

The Motion of an Azobenzene Light‐Controlled Switch: A Joint Theoretical and Experimental Approach

The Motion of an Azobenzene Light‐Controlled Switch: A Joint Theoretical and Experimental Approach

Dynamic Functional Molecular Systems: From Supramolecular Structures to Multi‐Component Machinery and to Molecular Cybernetics

A luminescent molecular turnstile

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