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Light-switchable buffer solutions based on merocyanine photoacids can be used as efficient photoenergy harvesting systems. Varying the solvation environment of merocyanine photoacids in water-methanol mixtures allows one to carefully tune their photoacidity, relaxation kinetics, and solubility, opening up the possibility to install persistent pH gradients of approximately 4 pH units under 500 nm light. When interfaced between two electrodes and exposed to asymmetric light irradiation, these solutions can be photoactivated precisely both in space and time, generating open circuit voltages as high as 240 mV that can last hours under steady-state irradiation - an outcome that is akin the peak performance of biological transmembrane proton pumps.
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http://dx.doi.org/10.1039/d4sc04833d | DOI Listing |
Adv Mater
July 2025
State Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei, Anhui, 230026, China.
Photomanipulation of the environmental pH plays a crucial role in modulating the reaction kinetics and engineering material functionalities. While conventional merocyanine photoacids offer pH modulability, their practical implementation is fundamentally constrained by aqueous dissolution and laborious regeneration. Here, a transformative strategy is reported through the covalent integration of merocyanine photoacids into hydrophilic polymer networks to construct regenerative photoacid matrices, which stably retain protons in the dark and spatiotemporally liberate them upon illumination.
View Article and Find Full Text PDFJ Phys Chem A
June 2025
University of Southern California, Los Angeles, California 90007, United States.
Water structure and proton dynamics in complex environments, such as mixed electrolytes, biological environments, and microdroplet surfaces, are often hypothesized to affect reaction thermodynamics, kinetics, and selectivity. Toward better understanding the influence of water microphases in complex mixtures, this study leverages the proton-dependent recovery kinetics of a merocyanine photoacid in acetonitrile (ACN) and dimethyl sulfoxide (DMSO) over a range of water mole fractions χ. We report that the rates of recovery, , do not scale linearly with χ.
View Article and Find Full Text PDFChem Commun (Camb)
April 2025
Institute of Organic Chemistry, Faculty of Chemistry and Pharmacy, University of Regensburg, Universitätsstraße 31, 93053 Regensburg, Germany.
Visible light-driven proton transfer is crucial in nature and catalysis. Here, we report that protic merocyanine-based photoswitches act as efficient and recyclable homogeneous Brønsted acid catalysts under blue or green light irradiation. Photo-promoted proton release efficiently enables Friedel-Crafts reactions with easy catalyst recovery and reuse.
View Article and Find Full Text PDFJACS Au
November 2024
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, P. R. China.
Precision synthesis of polyorganosiloxanes and temporal control over the polymerization process during ring-opening polymerization (ROP) of cyclosiloxanes remain challenging due to the occurrence of side reactions, e.g., intramolecular transfer (backbiting) and intermolecular chain transfer, and irreversible catalyst transformation.
View Article and Find Full Text PDFChem Sci
December 2024
Institut des Sciences et Ingénierie Chimiques, École Polytechnique Fédérale de Lausanne (EPFL) Lausanne 1015 Switzerland.
Light-switchable buffer solutions based on merocyanine photoacids can be used as efficient photoenergy harvesting systems. Varying the solvation environment of merocyanine photoacids in water-methanol mixtures allows one to carefully tune their photoacidity, relaxation kinetics, and solubility, opening up the possibility to install persistent pH gradients of approximately 4 pH units under 500 nm light. When interfaced between two electrodes and exposed to asymmetric light irradiation, these solutions can be photoactivated precisely both in space and time, generating open circuit voltages as high as 240 mV that can last hours under steady-state irradiation - an outcome that is akin the peak performance of biological transmembrane proton pumps.
View Article and Find Full Text PDF