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Folded-twisted mechanisms control dynamic redox properties, photophysics and electron transfer of anthanthrene-quinodimethanes.
Chem Sci
January 2025
Department of Physical Chemistry, University of Málaga, Andalucia-Tech Campus de Teatinos s/n 29071 Málaga Spain
The synthesis, electrochemical, spectroelectrochemical, photophysical and light induced electron transfer reactions in two new anthanthrene quinodimethanes have been studied and analyzed in the context of dynamic electrochemistry. Their properties are dependent on the interconversion between folded and twisted forms, which are separated by a relatively small energy range, thus allowing to explore their interconversion by variable temperature measurements. The photophysics of these molecules is mediated by a diradical excited state with a twisted structure that habilitates rapid intersystem crossing.
View Article and Find Full Text PDFVisible Light-Induced Organophotoredox-Catalyzed β-Hydroxytrifluoromethylation of Unactivated Alkenes.
J Org Chem
October 2024
Department of Chemistry, Indian Institute of Science Education and Research (IISER)-Pune, Dr. Homi Bhabha Road, Pashan, 411008 Pune, Maharashtra, India.
Herein, we report a mild transition metal-free organophotoredox-catalyzed approach for β-hydroxytrifluoromethylation of unactivated alkenes using CFSONa and acridinium salt. The protocol is compatible with various mono-, di-, and trisubstituted aliphatic unactivated alkenes containing numerous functional groups and natural product derivatives. Further, the postsynthetic modifications of the synthesized trifluoromethylated products have been demonstrated through cross-coupling and functional group interconversion reactions.
View Article and Find Full Text PDFPlant Phytochrome Interactions Decode Light and Temperature Signals.
Plant Cell
September 2024
Department of Biochemistry, University of Bayreuth, 95447 Bayreuth, Germany.
Plant phytochromes perceive red and far-red light to elicit adaptations to the changing environment. Downstream physiological responses revolve around red-light-induced interactions with phytochrome-interacting factors (PIF). Phytochromes double as thermoreceptors, owing to the pronounced temperature dependence of thermal reversion from the light-adapted Pfr to the dark-adapted Pr state.
View Article and Find Full Text PDFLight-Induced Electron Transfer in a [NiFe] Hydrogenase Opens a Photochemical Shortcut for Catalytic Dihydrogen Cleavage.
Angew Chem Int Ed Engl
October 2024
Fachbereich Physik, Freie Universität Berlin, Arnimallee 14, D-14195, Berlin, Germany.
[NiFe] hydrogenases catalyze the reversible cleavage of molecular hydrogen into protons and electrons. Here, we have studied the impact of temperature and illumination on an oxygen-tolerant and thermostable [NiFe] hydrogenase by IR and EPR spectroscopy. Equilibrium mixtures of two catalytic [NiFe] states, Ni-C and Ni-SR'', were found to drastically change with temperature, indicating a thermal exchange of electrons between the [NiFe] active site and iron-sulfur clusters of the enzyme.
View Article and Find Full Text PDFMicro-Ring Morphology of AgNCs and Light-Induced Reversible Interconversion of FCC AgNCs via Cu ions-Mediated Particle-Assisted Reversible Interconversion.
Angew Chem Int Ed Engl
October 2024
Department of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhopal Bypass Road, Bhauri, Bhopal, 462 066, Madhya Pradesh, India.
Article Synopsis
- - The study introduces a new technique called light-induced Particle-Assisted Reversible Interconversion (PARI) that allows for the reversible transformation of Face Centered Cubic (FCC) silver nanoclusters (AgNCs).
- - The research highlights the importance of plasmonic silver nanoparticles (AgNPs) in creating AgNCs with unique crystal structures and shapes through non-covalent interactions, leading to the formation of micro-ring architectures.
- - The findings demonstrate how the generation of AgNPs, enhanced by Cu ions, facilitates the growth and transformation of AgNCs, revealing a significant relationship between structure and properties in metal nanoclusters.
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