Arylimines offer promise in dynamic-covalent materials due to their recyclability and ease of synthesis. However, their light-triggered / isomerism has received little attention. This is attributed to challenges that include low thermal stability of their metastable state (<60 s at 20 °C), incomplete photoswitching (<50% to the metastable state), and the need for UV light (≤365 nm). We overcome these limitations with a novel class of imine photoswitch, the aryliminopyrazoles (AIPs). These AIPs can be switched using visible light (470 nm), attain photostationary states with over 95% of the -isomer, exhibit great resistance to fatigue, and have thermal half-lives up to 19.2 hours at room temperature. Additionally, they display T-type and negative photochromism under visible light irradiation-a useful property. The photochromic properties, quantitative assembly and accessibility of precursors set these photoswitches apart from their azo-based analogues. These findings open avenues for next-generation photoresponsive dynamic-covalent materials driven solely by these new photochromic linkages and further exploration of photocontrolled dynamic combinatorial chemistry.
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http://dx.doi.org/10.1039/d3sc05841g | DOI Listing |
J Am Chem Soc
November 2024
Department of Chemistry, Molecular Sciences Research Hub, Imperial College London, 82 Wood Lane, London W12 0BZ, U.K.
The incorporation of photoresponsive groups into porous materials is attractive as it offers potential advantages in controlling the pore size and selectivity to guest molecules. A combination of computational modeling and experiment resulted in the synthesis of two azobenzene-derived organic cages based on building blocks identified in a computational screen. Both cages incorporate three azobenzene moieties, and are therefore capable of 3-fold isomerization, using either ditopic or tetratopic aldehydes containing diazene functionality.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2024
Institut für Organische Chemie, Universität Würzburg, 97074, Würzburg, Germany.
Photoswitchable imines demonstrate light-dependent dynamic covalent chemistry and can function as molecular ratchets. However, the design of aryliminopyrazoles (AIPs) has been limited to N-pyrazole derivatives with ortho-pyrrolidine motifs. The impact of other functionalization patterns on the photoswitching properties remains unknown.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Institute of Advanced Materials and School of Chemistry and Chemical Engineering, Southeast University, Nanjing, 211189, China.
Developing visible-light-driven fluorescent photoswitches in the solid state remains an enormous challenge in smart materials. Such photoswitches are obtained from salicylaldimines through excited-state intramolecular proton transfer (ESIPT) and subsequent cis-trans isomerization strategies. By incorporating a bulky naphthalimide fluorophore into a Schiff base, three photoswitches achieve dual-mode changes (both in color and fluorescence) in the solid state.
View Article and Find Full Text PDFJ Am Chem Soc
July 2024
Institut für Organische Chemie, Universität Würzburg, Würzburg 97074, Germany.
Coupling a photochemical reaction to a thermal exchange process can drive the latter to a nonequilibrium steady state (NESS) under photoirradiation. Typically, systems use separate motifs for photoresponse and equilibrium-related processes. Here, we show that photoswitchable imines can fulfill both roles simultaneously, autonomously driving a dynamic covalent system into a NESS under continuous light irradiation.
View Article and Find Full Text PDFBioorg Chem
September 2024
Department of Organic Chemistry, Faculty of Chemistry, University of Seville, c/ Profesor García González 1, 41012 Sevilla, Spain. Electronic address:
The conventional approach to developing light-sensitive glycosidase activity regulators, involving the combination of a glycomimetic moiety and a photoactive azobenzene module, results in conjugates with differences in glycosidase inhibitory activity between the interchangeable E and Z-isomers at the azo group that are generally below one-order of magnitude. In this study, we have exploited the chemical mimic character of sp-iminosugars to access photoswitchable p- and o-azobenzene α-O-glycosides based on the gluco-configured representative ONJ. Notably, we achieved remarkably high switching factors for glycosidase inhibition, favoring either the E- or Z-isomer depending on the aglycone structure.
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