Tailoring the optical and dynamic properties of iminothioindoxyl photoswitches through acidochromism

Medveď, Miroslav; Hoorens, Mark W. H.; Donato, Mariangela Di; Laurent, Adèle D.; Fan, Jiayun; Taddei, Maria Letizia; Hilbers, Michiel; Feringa, Ben L.; Buma, Wybren Jan; Szymański, Wiktor

doi:10.1039/d0sc07000a

Cited by 21 publications

(15 citation statements)

References 54 publications

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“…To our best knowledge, such a feature has not been observed in photoswitchable systems before. It is also fundamentally different from earlier reported examples of acid-gated photoresponsivity, 37,[39][40][41] which allowed both switching directions in one of the states. In our case, only a single (and opposite for neutral and protonated forms) direction of photoswitching is suppressed, affording quantitative conversion by default.…”

Section: Monodirectional Photoisomerization Cyclecontrasting

confidence: 98%

Monodirectional photocycle drives proton translocation

Duindam

Dongen

Siegler

et al. 2023

Preprint

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Photoisomerization of retinal is pivotal to ion translocation across the bacterial membrane and has served as inspiration for the development of artificial molecular switches and machines. Light-driven synthetic systems in which a macrocyclic component transits along a nonsymmetric axle in a specific direction have been reported, however, unidirectional and repetitive translocation of small substrates, including ions, has not been achieved. Herein, we describe unique protonation-controlled isomerization behavior for hemi-indigo dyes bearing N-heterocycles, owing to intramolecular hydrogen bond formation. Light-induced isomerization from Z to E isomer is unlocked when protonated, while reverse E→Z photoisomerization occurs in the neutral state. As a consequence, associated protons are displaced in one direction with respect to the photoswitchable scaffold. We foresee that selective inhibition of photoswitching paths by substrate binding can be applied as general method toward directional transport and pumping of that substrate, which will prove critical in developing artificial systems in which concentration gradients can be effectively generated using (solar) light energy.

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Section: Monodirectional Photoisomerization Cyclecontrasting

confidence: 98%

Monodirectional photocycle drives proton translocation

Duindam

Dongen

Siegler

et al. 2023

Preprint

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“… 252 Addition of acid lead to protonation of the C N bond and enforced an altered isomerization pathway simultaneously prolonging the thermal half-life of the switch to the second–minute range. 287 The photochemical process in the neutral ITI can be triggered in a wide range of solvents, was also observed in buffer (1.7–6.7% DMSO for solubilization, depending on the substituents), and remained unaltered in the presence of the cellular reducing-agent glutathione. 252 …”

Section: Molecular Photoswitchesmentioning

confidence: 98%

Molecular photoswitches in aqueous environments

et al. 2021

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“…E-FCA was found to be visibly fluorescent on the entire pH range studied (pH 2.0-12.0), with the maxima of the emission spectra being pH-dependent. Hence, although not characterized with significant fluorescence quantum yields, E-FCA might be considered as an acido-/basochromic fluorophore in a similar manner to some other compounds previously reported [41][42][43].…”

Section: Discussionmentioning

confidence: 83%

pH-Dependent Photoinduced Interconversion of Furocoumaric and Furocoumarinic Acids

et al. 2021

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Photo-controlled or photo-regulated molecules, especially biologically active and operating in physiological conditions, are in steady demand. Herein, furocoumaric and furocoumarinic acids being (Z/E)-isomers relative to each other were obtained in two stages starting from psoralen: the alkaline solvolysis of psoralen led to furocoumaric acid, which was further Z → E photoisomerized (365 nm) to furocoumarinic acid. The kinetics of Z → E photoisomerization was monitored by HPLC and UV-vis spectrophotometry. Photophysical characteristics in the aqueous phase for both acids, as well as the reversibility of (Z/E) photoisomerization process, were also assessed. Furocoumarinic acid was found to be visibly fluorescent at pH 2.0–12.0, with the maxima of fluorescence emission spectra being pH-dependent. The reverse E → Z photoisomerization predicted by quantum chemistry calculations as energetically favorable for the monoanionic form of furocoumarinic acid was proved in the experiment while being complicated by pyrone ring closure back to psoralen in acidic and neutral conditions. The preparative synthesis of furocoumarinic acid outlined in this work is particularly valuable in view of a wide range of pharmacological effects previously predicted for this compound.

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Tailoring the optical and dynamic properties of iminothioindoxyl photoswitches through acidochromism

Abstract: Multi-responsive functional molecules are key for obtaining user-defined control of the properties and functions of chemical and biological systems. In this respect, pH-responsive photochromes, whose switching can be directed with...

Cited by 21 publications

References 54 publications

Monodirectional photocycle drives proton translocation

Monodirectional photocycle drives proton translocation

Molecular photoswitches in aqueous environments

pH-Dependent Photoinduced Interconversion of Furocoumaric and Furocoumarinic Acids

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