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Assembling chiral and magnetic units at a molecular level is a key to achieving a strong magneto-optical (MO) effect, especially for lanthanide complexes with a specific 4 electronic configuration. However, the - transitions are generally restricted by selection rules, making the observation of the MO response extremely challenging. Herein, we reported the synthesis of two highly air-stable chiral Dy complexes and , with a pair of tailored chelating chiral ligands. Besides magnetization dynamics in a wide temperature range, the magnetic circular dichroism (MCD) of and shows remarkable MO responses of - transitions of Dy centers in the vis-NIR region, and CD spectra of and provide the first experimental observation of room-temperature CD peaks corresponding to the - transition of Dy at 450 nm. Importantly, the direction of CD signals from 700 to 1100 nm can be reversibly switched by external magnetic fields. Mechanism study reveals that the strong magnetic anisotropy of the Dy center is a key to inducing the remarkable room-temperature MO effect. This work not only provides a facile way to construct air-stable magnetic and chiral complexes but also gains insights into the influence of magnetic anisotropy on the strong MO effect in a wide spectrum range at room temperature.
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http://dx.doi.org/10.1021/jacs.5c04297 | DOI Listing |
Angew Chem Int Ed Engl
September 2025
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
The enantioselective construction of quaternary carbon stereocenters bearing amine functionalities represents a significant challenge in organic synthesis despite their prevalence in pharmaceutically active compounds. Herein, we report a versatile metallaphotoredox platform for the asymmetric incorporation of amine fragments onto quaternary carbons via coupling of alkene-tethered aryl bromides with readily available α-silylamines. This transformation proceeds under mild conditions without requiring organometallic reagents or stoichiometric reductants.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2025
CFisUC, Department of Physics, University of Coimbra, 3004-516, Coimbra, Portugal.
With the goal of manipulating (bio)chemical processes, photoswitches emerge as important assets in molecular nanotechnology. To guide synthetic strategies toward increasingly more efficient systems, conformational dynamics studies performed with atomic rigor are in demand, particularly if this information can be extracted with control over the size of a perturbing solvation layer. Here, we use jet-cooled rotational spectroscopy and quantum chemistry calculations to unravel the structure and micro-hydration dynamics of a prototype photoswitch.
View Article and Find Full Text PDFNat Commun
September 2025
Institute for Theoretical Physics, University of Regensburg, Regensburg, Germany.
The nature of the dominant pairing mechanism in some two-dimensional transition metal dichalcogenides is still debated. Focusing on monolayer 1H-NbSe, we show that superconductivity can be induced by the Coulomb interaction when accounting for screening effects on the trigonal lattice with multiple orbitals. Using ab initio based tight-binding parametrizations for the relevant low-energy d-bands, we evaluate the screened interaction microscopically.
View Article and Find Full Text PDFChem Commun (Camb)
September 2025
Department of Chemistry, Biochemistry and Pharmaceutical Sciences, University of Bern, CH-3012 Bern, Switzerland.
Iron complexes bearing chiral salicyloxazoline (Salox) ligands catalyze the enantioselective intramolecular C-H bond amination of alkyl azides, reaching 58-76% ee for benzylic C-H bonds. Further, for the first time aliphatic C-H bond amination is demonstrated (∼40% ee). This class of catalysts even activates primary aliphatic C-H bonds, albeit with moderate ee.
View Article and Find Full Text PDFChemSusChem
September 2025
Organic Chemistry Institute, University of Münster, Corrensstraße 36, 48149, Münster, Germany.
A three-step, one-pot, sequential cascade starting from simple feedstocks to increase complexity toward value-added chiral synthetic building blocks is reported. This is achieved by precisely integrating organic photocatalysis and noncovalent organocatalysis, often operating at dissimilar conditions and reaction media. In particular, this strategy is used to enable the direct transformation of readily available benzylic substrates, such as methylbenzenes, benzyl alcohols, or amines, into enantioenriched α-aminonitriles by benzylic CH photooxidation to their corresponding aldehydes, followed by in situ imine formation and final asymmetric organocatalytic Strecker reaction.
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