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We present a novel light-locked dynamic covalent polymerization methodology to synthesize conjugated polymers based on BisAzaCoroneneDiimides (BACDs). This metal-free process converts reversible poly imines into kinetically locked conjugated polymers using visible light, generating minimal side products. By incorporating aldehyde-functionalized comonomers, the approach enables the creation of diverse n-type semiconducting polymers with tunable optical band gaps and low LUMO levels. The polymers exhibit exceptional thermal, electrochemical, and photostability with strong interchain interactions upon electrochemical reduction observed in solution, attributed to the BACD core. Broad absorption from the visible to the near-infrared range underscores their potential in charge and energy transport applications for organic electronics. This scalable, sustainable strategy unlocks access to a versatile class of n-type diimide polymers.
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http://dx.doi.org/10.1021/jacs.5c01351 | DOI Listing |
J Am Chem Soc
September 2025
State Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China.
The discovery of new weak supramolecular interactions and supramolecular synthons is essential for directing self-assembly processes with enhanced precision, diversity, and functionality in complex molecular architectures. Here, we report the controlled self-assembly of diverse supramolecular architectures by a new directional bonding approach through the integration of radical-based dynamic covalent chemistry and supramolecular synthons. A novel macrocyclic synthon, , with a linear direction is constructed via radical-based dynamic covalent bonds from the phenothiazine building block substituted with two dicyanomethyl radicals.
View Article and Find Full Text PDFACS Macro Lett
September 2025
Pritzker School of Molecular Engineering, The University of Chicago, Chicago, Illinois 60637, United States.
Introducing dynamic covalent chemistries into polymer networks allows access to complex linear viscoelasticity, owing to the reversible nature of the dynamic bonds. While this macroscopic mechanical behavior is influenced by the dynamic exchange of these chemistries, connecting the microscopic dynamics to the bulk properties is hindered by the time scale conventional techniques can observe. Here, light scattering passive microrheology is applied to probe short-time dynamics of dynamic covalent networks that consist of telechelic benzalcyanoacetate (BCA) Michael acceptors and thiol-functionalized cross-linkers.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2025
College of Smart Materials and Future Energy, Fudan University, Songhu Road 2005, Shanghai, 200438, P.R. China.
Solar-driven photocatalytic oxygen reduction reaction using covalent organic frameworks (COFs) offers a promising approach for sustainable hydrogen peroxide (HO) production. Despite their advantages, the reported COFs-based photocatalysts suffer insufficient photocatalytic HO efficiency due to the mismatched electron-proton dynamics. Herein, we report three one-dimensional (1D) COF photocatalysts for efficient HO production via the hydrogen radical (H•) mediated concerted electron-proton transfer (CEPT) process.
View Article and Find Full Text PDFNat Commun
September 2025
Center for Advancing Electronics Dresden & Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, Dresden, Germany.
The synthesis of thin crystalline two-dimensional polymers (2DPs) typically relies on reversible dynamic covalent reactions. While substantial progress has been made in solution-based and interfacial syntheses, achieving 2DPs through irreversible carbon-carbon coupling reactions remains a formidable challenge. Herein, we present an on-liquid surface (a mixture of N,N-dimethylacetamide and water, DMAc-HO) synthesis method for constructing diyne-linked 2DP (DY2DP) crystals via Glaser coupling, assisted by a perfluoro-surfactant (PFS) monolayer.
View Article and Find Full Text PDFJ Phys Chem B
September 2025
School of Science, RMIT University, Melbourne 3000, Australia.
Pentameric ligand-gated ion channels control synaptic neurotransmission via an allosteric mechanism, whereby agonist binding induces global protein conformational changes that open an ion-conducting pore. For the proton-activated bacterial () ligand-gated ion channel (GLIC), high-resolution structures are available in multiple conformational states. We used a library of atomistic molecular dynamics (MD) simulations to study conformational changes and to perform dynamic network analysis to elucidate the communication pathways underlying the gating process.
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