Getting a molecular grip on the half-lives of iminothioindoxyl photoswitches

Visible-light-operated photoswitches are of growing interest in reversibly controlling molecular processes, enabling for example the precise spatiotemporal focusing of drug activity and manipulating the properties of materials. Therefore, many research efforts have been spent on seeking control over...

Full description

Saved in:

Bibliographic Details
Published in:	Chemical science (Cambridge) Vol. 15; no. 35; pp. 14379 - 14389
Main Authors:	Boëtius, Melody E, Hoorens, Mark W H, Ošťadnický, Martin, Laurent, Adèle D, di Donato, Mariangela, van Wingaarden, Aldo C A, Hilbers, Michiel F, Feringa, Ben L, Buma, Wybren Jan, Medveď, Miroslav, Szymanski, Wiktor
Format:	Journal Article
Language:	English
Published:	England Royal Society of Chemistry 26-07-2024 The Royal Society of Chemistry
Subjects:	Aromatic compounds Chemistry Functional groups Half-life Material properties Metastable state Physical properties Thermal stability Thermodynamic properties
Online Access:	Get full text
Tags:	Add Tag No Tags, Be the first to tag this record!

Description
Summary:	Visible-light-operated photoswitches are of growing interest in reversibly controlling molecular processes, enabling for example the precise spatiotemporal focusing of drug activity and manipulating the properties of materials. Therefore, many research efforts have been spent on seeking control over the (photo)physical properties of photoswitches, in particular the absorption maxima and the half-life. For photopharmacological applications, photoswitches should ideally be operated by visible light in at least one direction, and feature a metastable isomer with a half-life of 0.1-10 seconds. Here we present our efforts towards the engineering of the half-life of iminothioindoxyl (ITI) photoswitches, a recently discovered class of visible-light-responsive photochromes, whose applicability was hitherto limited by half-lives in the low millisecond range. Through the synthesis and characterization of a library of ITI photoswitches, we discovered variants with a substantially increased thermal stability, reaching half-lives of up to 0.2 seconds. Based on spectroscopic and computational analyses, we demonstrate how different substituent positions on the ITI molecule can be used to tune its photophysical properties independently to fit the desired application. Additionally, the unique reactivity of the ITI derivative that featured a perfluoro-aromatic ring and had the most long-lived metastable state was shown to be useful for labeling of nucleophilic functional groups. The present research thus paves the way for using ITI photoswitches in photopharmacology and chemical biology.
Bibliography:	ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23
ISSN:	2041-6520 2041-6539
DOI:	10.1039/d4sc01457j