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The very first representative of trithia-bridged N-heterotriangulene, a triphenylamine with sulfur atoms bridging the ortho-positions, was synthesized by a sequence of regioselective sulfenylation with phthalimidesulfenyl chloride followed by Lewis acid-catalyzed electrophilic cyclization. X-ray crystallography revealed a saddle-shaped geometry of the polycyclic scaffold. UV/Vis absorption spectroscopy and cyclic voltammetry were used to characterize the optoelectronic properties. The title compound is a particularly strong electron donor forming a perfectly stable radical cation, which was analyzed by electron paramagnetic resonance spectroscopy and X-ray crystallography. The electron donor properties were further highlighted by the formation of crystalline donor-acceptor complexes with strong cyano-based acceptors.
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http://dx.doi.org/10.1002/anie.202423802 | DOI Listing |
Chem Sci
August 2025
College of Chemistry and Materials Science, Key Laboratory of Chemical Biology of Hebei Province, Hebei Research Center of the Basic Discipline of Synthetic Chemistry, Institute of Life Science and Green Development Hebei University Baoding Hebei 071002 P. R. China
The photocatalytic oxidative dipolar [3 + 2] cycloaddition reaction is a promising green approach for producing pyrrolo[2,1-]isoquinolines. However, developing sustainable cycloaddition methods with heterogeneous photocatalysts is still in its infancy, largely owing to their low reactivity and photostability. Herein, we propose a charge-oxygen synergy strategy through a dual-engineered covalent organic framework (COF) by integrating π-spacers with donor-acceptor motifs to promote intermolecular cycloaddition.
View Article and Find Full Text PDFACS Omega
September 2025
International Centre for Materials Science, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur- P.O., Bangalore 560064, India.
Lambert and co-workers have developed several chiral bases using a cyclopropeneimine as the basic moiety. Typically, these catalysts have a pendant hydroxyl group which acts as a hydrogen-bond donor and activates the electrophile. In catalysts with a hydrogen-bond donor, prior work from the Sigman group has shown that the acidity of the donor plays an important role in imparting selectivity.
View Article and Find Full Text PDFNatl Sci Rev
August 2025
Center for AIE Research, Shenzhen Key Laboratory of Polymer Science and Technology, Guangdong Provincial Key Laboratory of New Energy Materials Service Safety, College of Material Science and Engineering, Shenzhen University, Shenzhen 518060, China.
Multimodal phototheranostics has been recognized as one of the most momentous advances in cancer treatment. Of particular interest is a single molecular species simultaneously featuring in multiple imaging and synergistic phototherapies; the development of such a molecular species is nevertheless a formidably challenging task. Herein, we innovatively designed and synthesized three aggregation-induced emission (AIE)-active molecules with emission in the second near-infrared (NIR-II) window, by employing 10-indeno[1,2-][1,2,5]thiadiazolo[3,4-]quinoxalin-10-one as the electron acceptor, 4-(-butyl)--(4-(-butyl)phenyl)--phenylaniline as the electron donor, and different π-bridge moieties.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2025
Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA, 15213, USA.
α-Lipoic acid (LA) has recently emerged as an attractive, inexpensive monomer for synthesizing degradable polymers via ring-opening of its 1,2-dithiolane, introducing easily cleavable disulfide linkages into polymer backbones. Reversible addition-fragmentation chain transfer (RAFT) copolymerization with vinyl monomers enables access to degradable poly(disulfide)s with controlled molecular weights. However, conventional thermal RAFT methods suffer from oxygen sensitivity, limited LA incorporation (<40 mol%), and modest degrees of polymerization (DP < 300).
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China.
Cross-electrophile coupling (XEC) reactions are considered to be among the most fundamental construction of carbon-carbon bonds in organic chemistry. Traditionally, stoichiometric reductants, including metallic and organic reagents, are required to promote these conversions, resulting in significant waste that contributes to environmental pollution and increased disposal costs. In this study, we report a divided electrochemical synthesis-based cross-coupling platform in which HO is oxidized at the anode surface to generate electrons that produce a lower oxidation state nickel catalyst on the cathode surface, enabling XEC reactions without the need for metallic or organic reagents.
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