Photoacid generators (PAGs) are invaluable molecular tools that exhibited tremendous potential in emerging interdisciplinary researches of life-science, nanotechnology and smart materials. However, current PAGs are primarily mono-functional in terms of acid generation and rely on UV/deep-blue light excitation, posing a fundamental hurdle to their broader adoption. Developing cooperatively functioned PAGs with long-wavelength light responsiveness presents a formidable challenge due to the absence of suitable molecular scaffolds. Here, we introduce a newly-developed perylene bisimides PAG motif (PBI-PAG) that integrates desired multi-functionality and visible-light photo-reactivity. Taking advantages of characteristic opto-electronic properties of PBI scaffold, PBI-PAGs are capable of quantitative releasing (> 99%) a palette of acids upon green/red light (560-605 nm) excitation. Concurrently, a photo-generated counterpart is functioned as a photo-sensitizer that could perform cooperatively with acid as an anti-metastasis cancer therapy agent. These two processes constitute the first example of a cooperatively functioned PAG operated at substrate-adaptive wavelengths.
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http://dx.doi.org/10.1002/anie.202425313 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
East China University of Science and Technology, School of Chemistry and Molecular Engineering, CHINA.
Photoacid generators (PAGs) are invaluable molecular tools that exhibited tremendous potential in emerging interdisciplinary researches of life-science, nanotechnology and smart materials. However, current PAGs are primarily mono-functional in terms of acid generation and rely on UV/deep-blue light excitation, posing a fundamental hurdle to their broader adoption. Developing cooperatively functioned PAGs with long-wavelength light responsiveness presents a formidable challenge due to the absence of suitable molecular scaffolds.
View Article and Find Full Text PDFJ Org Chem
January 2025
Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati, Assam 781039, India.
The photoacid-catalyzed synthesis of 2-deoxy glycosides is presented using stable glycosyl -[1-(-MeO-Phenyl)vinyl]benzoate (PMPVB) donors and employing the eosin Y and diphenyl disulfide (PhSSPh) catalytic system in the presence of blue LED lights. The remote activation of the alkene functionality under the photoacid catalysis followed by a 5-- cyclization led to the generation of oxocarbenium ions that were trapped to provide the glycosylated products in excellent yields and decent selectivities under mild conditions. This method is also useful for the photoacid-catalyzed synthesis of -methoxybenzyl-alkyl ethers.
View Article and Find Full Text PDFChem Sci
January 2025
Institut für Physikalische und Theoretische Chemie, Universität Regensburg 93040 Regensburg Germany +49 941 943 4487.
Photoacids undergo an increase in acidity upon electronic excitation, enabling excited-state proton transfer (ESPT) reactions. A multitude of compounds that allow ESPT has been identified and integrated in numerous applications, as is outlined by reviewing the rich history of photoacid research reaching back more than 90 years. In particular, achievements together with ambitions and challenges are highlighted from a combined experimental and theoretical perspective.
View Article and Find Full Text PDFACS Cent Sci
November 2024
Department of Chemistry, Cornell University, Ithaca, New York 14853, United States.
The synthesis of polymeric thermoset materials with spatially controlled physical properties using readily available resins is a grand challenge. To address this challenge, we developed a photoinitiated polymerization method that enables the spatial switching of radical and cationic polymerizations by controlling the dosage of monochromatic light. This method, which we call Switching Polymerizations by Light Titration (SPLiT), leverages the use of substoichiometric amounts of a photobuffer in combination with traditional photoacid generators.
View Article and Find Full Text PDFChem Sci
December 2024
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University Xi'an 710119 China
Photoacid generators (PAGs) and photohydride generators (PHGs) are specific photolabile protecting groups that release acid and hydride, respectively. Over the past decade, great efforts have been devoted to developing novel PAGs and PHGs with advanced efficiency, among which, two of the promising candidates are diarylethene (DAE)-based PAGs and PHGs, which release acids/hydrides during photochromic electrocyclization. The release quantum yield for PAGs is acceptable, while that of PHGs is only 4.
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