We report a bottom-up synthesis of a photochemically and thermally active azobenzene-based polyelectrolyte multilayer (PEM) planar defect embedded in a colloidal photonic crystal (CPC). Both photoisomerization and thermal cycling lead to a precise tuning of an intragap transmitting state induced by the PEM structural defect.
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http://dx.doi.org/10.1021/ja0521573 | DOI Listing |
Molecules
January 2025
Leicester School of Pharmacy, De Montfort University, The Gateway, Leicester LE1 9BH, UK.
Photothermal reactions, involving both photochemical and thermal reaction steps, are the most abundant sequences in photochemistry. The derivation of their rate laws is standardized, but the integration of these rate laws has not yet been achieved. Indeed, the field still lacks integrated rate laws for the description of these reactions' behavior and/or identification of their reaction order.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
Department of Chemistry - Ångström Laboratory, Uppsala University, Box 523, Uppsala 751 20, Sweden.
Understanding and controlling molecular motions is of pivotal importance for designing molecular machinery and functional molecular systems, capable of performing complex tasks. Herein, we report a comprehensive theoretical study to elucidate the dynamic behavior of a bis(benzoxazole)-based overcrowded alkene displaying several coupled and uncoupled molecular motions. The benzoxazole moieties give rise to 4 different stable conformers that interconvert through single-bond rotations.
View Article and Find Full Text PDFACS Catal
January 2025
Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, United Kingdom.
An aryl radical assay is used to provide information about the formation of aryl radicals from aryl halides in coupling reactions to arenes in the presence of palladium sources and under LED irradiation (λ = 456 nm). The assay uses 2-halo--xylenes as substrates. Aryl radical formation is indicated both by a defined product composition and by signature deuterium isotope effects.
View Article and Find Full Text PDFMacromolecules
January 2025
Department of Chemistry and Biochemistry, Miami University, 651 E High St, Oxford, Ohio 45056, United States.
Photochemical processes are often thought to be temperature-independent. However, photochemical polymerization involves photochemical processes such as light-driven radical generation coupled with thermal-driven reactions such as monomer propagation. The apparent activation energy of propagation, ( ), of a series of three monomers, methyl acrylate (MA), methyl methacrylate (MMA), and styrene (STY), are deduced from Arrhenius analysis of conventional and RAFT photopolymerization of these monomers across a range of corresponding temperatures.
View Article and Find Full Text PDFNat Chem
January 2025
Department of Chemistry, University of California Irvine, Irvine, CA, USA.
Controlling reaction outcomes through external influences is a central goal in chemistry. Vibrational coupling between molecular vibrations and cavity modes is rapidly emerging as a distinct strategy compared with conventional thermochemical and photochemical methods; however, insight into the fundamental mechanisms remains limited. Here we investigate how vibrational weak and strong coupling in plasmonic nanocavities modifies the thermal dehydration of copper sulfate pentahydrate.
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