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Multi-resonance emitters with room-temperature phosphorescence in amorphous state and excited by visible light.
Chem Sci
November 2024
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences Changchun 130022 P. R. China
Unlike boron, nitrogen-containing multi-resonance emitters with thermally activated delayed fluorescence, here we report boron, sulfur (B, S)-based multi-resonance emitters with room-temperature phosphorescence (RTP) by inserting thiophene into a 5,9-dithia-13-boranaphtho[3,2,1-]anthracene skeleton that simultaneously realizes large singlet-triplet energy splitting and strong spin-orbital coupling, leading to efficient room-temperature phosphorescence in an amorphous state. Unlike most RTP emitters with ultraviolet excitation, the multi-resonance RTP emitters exhibit strong phosphorescence under daily-use blue/white LED lamps owing to their intense absorption in the visible-light region (400-486 nm). Meanwhile, such RTP behavior can be tuned by the number and fusing pattern of the thiophene moieties, with the emitters containing thiophene linked to boron atoms α-positions exhibiting bathochromatically shifted emissions and longer phosphorescence lifetimes (47.
View Article and Find Full Text PDFSuperstructures of copper nanoclusters as NIR TADF emitters: solvent-dependent optical and morphological modulation.
Nanoscale
November 2024
Department of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhopal Bypass Road, Bhauri, Bhopal 462 066, Madhya Pradesh, India.
Herein, we report 2-mercaptopyridine-templated copper nanoclusters (CuNCs) which display near infra-red (NIR) emission, both in the solid and colloidal states. Interestingly, the NIR emission can be modulated to orange emission by preparing the CuNCs in a mixed solvent system of chloroform and methanol instead of water. The drastic change in the photo-physical properties of the CuNCs when prepared in two different solvent systems is accompanied by a unique morphological tuning.
View Article and Find Full Text PDFConformational Tuning of Magnetic Interactions in Coupled Nanographenes.
Nano Lett
October 2024
nanotech@surfaces Laboratory, Empa─Swiss Federal Laboratories for Materials Science and Technology, 8600 Dübendorf, Switzerland.
Article Synopsis
- Phenalenyl (CH) is a type of nanographene that features a unique open-shell structure with spin-1/2 properties, revealing interesting electrical behavior when studied through techniques like STM-IETS.
- Researchers have discovered that the exchange interactions in phenalenyl dimers can be adjusted by changing the angle between the two molecules, which can lead to different electronic properties.
- The study employs various theoretical approaches, including density functional theory, to explore ways to manipulate twisting in these dimers, potentially enabling control over magnetic couplings in carbon-based structures.
Singlet-Triplet Inversions in Through-Bond Charge-Transfer States.
J Phys Chem Lett
October 2024
Laboratory for Computational Molecular Design, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland.
Molecules where the lowest excited singlet state is lower in energy than the lowest triplet are highly promising for a number of organic materials applications as efficiency limitations stemming from spin statistics are overcome. All molecules known to possess such singlet-triplet inversions exhibit a pattern of spatially alternating but nonoverlapping HOMO and LUMO orbitals, meaning the lowest excited states are of a local character. Here, we demonstrate that derivatives of the bicyclic hydrocarbon calicene exhibit Hund's rule violations in charge-transfer (CT) states between its rings.
View Article and Find Full Text PDFTuning Electron Transfer Coupling and Exchange Interaction in Bis-triarylamine Radical Cations and Dications by Bridge Electron Density.
J Am Chem Soc
October 2024
Institut für Organische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
The influence of the electron density of a bridge connecting two redox centers on both the intervalence hole transfer and the magnetic superexchange was investigated in a series of bridged bis-triarylamine mono- and dications. In this series, the bridge was 2,7-fluorenyl, where the bridge electron density was modified by substituents at the 9-position. For the mixed-valence monocations, the observation of both an intervalence charge transfer (IVCT) band and an absorption band associated with an electron transfer from the bridging fluorene to the triarylamine radical cation centers allowed determination of the electron transfer couplings in the framework of the three-state generalized Mulliken-Hush theory.
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