The title trianion reacts successively with cationic transition-metal fragments to afford a heterotrimetallic Mn-Mo-Pt species.
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http://dx.doi.org/10.1039/b505841d | DOI Listing |
Int J Mol Sci
November 2024
Institute of Natural Products and Cosmetics, Faculty of Biotechnology and Food Sciences, Lodz University of Technology, Stefanowskiego 2/22, 90-537 Lodz, Poland.
In this study, the DFT/M062X/PCM method was applied to investigate thermodynamic and kinetic aspects of reactions involved in possible mechanisms of antioxidant activity of caffeic acid against HOO radicals in aqueous medium at different pH values. Kinetic parameters of the reactions involved in HAT (Hydrogen Atom Transfer), RAF (Radical Adduct Formation), and SET (Single Electron Transfer) mechanisms, including reaction energy barriers and bimolecular rate constants, were determined, and identification and characterization of stationary points along the reaction pathways within HAT and RAF mechanisms were performed. Inspection of geometrical parameters and spin densities of the radical products formed within HAT and RAF mechanisms revealed that they are stabilized by hydrogen bonding interactions and the odd electron originated through the reaction with the HOO radical is spread over the entire molecule, resulting in significant radical stabilization.
View Article and Find Full Text PDFDalton Trans
January 2025
School of Chemistry, University of Glasgow, University Avenue, Glasgow, G12 8QQ, UK.
We enhance single-ion magnet (SIM) magnetisation reversal barriers by engineering the second coordination sphere, substituting conventional small monoanions with a bulky polyoxometalate (POM) trianion. Importantly, our approach serves as a model for creating new high-performance multifunctional hybrid materials.
View Article and Find Full Text PDFLytic Polysaccharide Monooxygenases (LPMOs) catalyze the oxidative depolymerization of polysaccharides at a monocopper active site, that is coordinated by the so-called histidine brace. In the past, this motif has sparked considerable interest, mostly due to its ability to generate and stabilize highly oxidizing intermediates during catalysis. We used a variety of advanced EPR techniques, including Electron Nuclear Double Resonance (ENDOR), Electron Spin Echo Envelope Modulation (ESEEM) and Hyperfine Sublevel Correlation (HYSCORE) spectroscopy in combination with isotopic labelling (N, H) to characterize the active site of the bacterial LPMO AA10A over a wide pH range (pH 4.
View Article and Find Full Text PDFCryst Growth Des
November 2024
School of Biological and Chemical Sciences, University of Galway, Galway H91TK33, Ireland.
In the field of cocrystals, the synthon-based design of two-component crystals is well established and the interest is now shifting toward higher order cocrystals as the next challenge. Carboxylic acids form a robust synthon with pyridyl coformers and interact with 2-aminopyrimidines through a pair of strong, charge-assisted hydrogen bonds. In this work we describe the formation of higher order salts and salt cocrystals of trimesic acid using 2,4-diaminopyrimidine (pyrimethamine, trimethoprim) and pyridyl (4,4'-bipyridine, 1,2-di(4-pyridyl)ethylene, 1,3-di(4-pyridyl)propane, 4-phenylpyridine) coformers.
View Article and Find Full Text PDFInorg Chem
November 2024
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
We report the synthesis and characterization of tris(biphenyl-2,2'-diyl)metal complexes of trivalent group 9 elements (, M = Co, Rh, Ir) and their nonplanarly π-extended analogs, tris(1,1'-binaphthyl-2,2'-diyl)metal complexes (, M = Rh, Ir). Single crystal X-ray crystallography reveals the distorted octahedral geometry with an approximate symmetry of trianionic complexes (M = Co, Rh, Ir) and (M = Rh, Ir), which are contacted by three Li ions in the crystal. Complex exhibits yellow luminescence in THF with a photoluminescence quantum yield () of up to 0.
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