The oxidation potential of thioethers constrained to be near aromatic rings is lowered, due to an antibonding interaction between the p-type sulfur lone pair with the neighboring phenyl π-system which on removal of an electron becomes a new kind of 3-electron S∴π bonding that reveals itself in the photoelectron spectrum and by an electronic transition involving the orbitals participating in the S∴π bond.
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http://dx.doi.org/10.1021/ol402126f | DOI Listing |
Nat Commun
January 2025
Department of Physics, University of Michigan, Ann Arbor, MI, USA.
Excitons, bound electron-hole pairs, influence the optical properties in strongly interacting solid-state systems and are typically most stable and pronounced in monolayer materials. Bulk systems with large exciton binding energies, on the other hand, are rare and the mechanisms driving their stability are still relatively unexplored. Here, we report an exceptionally large exciton binding energy in single crystals of the bulk van der Waals antiferromagnet CrSBr.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
College of Science and Engineering, Flinders University, GPO Box 2100, Adelaide, SA 5001, Australia.
We report the results of a study of the interaction between torsion and the low frequency out-of-plane silyl wag vibration in the ground, S, and excited, S, electronic states of phenylsilane. These studies follow the observation of interactions between methyl torsion and the out-of-plane methyl wagging vibration in toluene, several fluoro-substituted toluenes and -methylpyrrole. The interaction leads to various spectroscopic constants becoming divorced from their usual physical meaning.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, Texas A&M University, College Station, Texas 77843, United States.
Terminal metal-phosphorus (M-P) complexes are of significant contemporary interest as potential platforms for P-atom transfer (PAT) chemistry. Decarbonylation of metal-phosphaethynolate (M-PCO) complexes has emerged as a general synthetic approach to terminal M-P complexes. M-P complexes that are stabilized by strong M-P multiple bonds are kinetically persistent and isolable.
View Article and Find Full Text PDFACS Chem Neurosci
January 2025
School of Molecular and Life Sciences, Faculty of Science and Engineering, Curtin University, Bentley, WA 6845, Australia.
Natural aging is associated with mild memory loss and cognitive decline, and age is the greatest risk factor for neurodegenerative diseases, such as Alzheimer's disease. There is substantial evidence that oxidative stress is a major contributor to both natural aging and neurodegenerative disease, and coincidently, levels of redox active metals such as Fe and Cu are known to be elevated later in life. Recently, a pronounced age-related increase in Cu content has been reported to occur in mice and rats around a vital regulatory brain region, the subventricular zone of lateral ventricles.
View Article and Find Full Text PDFACS Appl Mater Interfaces
January 2025
RIKEN Center for Emergent Matter Science (CEMS), 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.
A fluoroalkyl-containing electron acceptor (Y-SSM) is designed and synthesized to control the orientation of the benchmark non-fullerene acceptor Y6 in thin films. Due to the low surface energy of the two fluoroalkyl chains at the terminal part of Y-SSM, it spontaneously segregates to the film surface during spin coating, forming a monolayer of edge-on oriented Y-SSM. The Y-SSM monolayer leads to crystallization of the underlying Y6 to induce a standing-up orientation in the bulk of the films, which is strikingly different from pure Y6 films that tend to be a face-on orientation.
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