Towards single-crystalline two-dimensional poly(arylene vinylene) covalent organic frameworks
Year: 2026
Type: article
Abstract: Vinylene-linked two-dimensional (2D) conjugated covalent organic frameworks, or 2D poly(arylene vinylene)s (2D PAVs), are promising polymer semiconductors for (opto-)electronics, photocatalysis and electrochemistry. However, conventional solvothermal synthesis often produces 2D PAVs that are poorly crystalline or difficult to access. Here we introduce a Mannich-elimination strategy that converts 8 2D imine-covalent organic frameworks into 11 highly crystalline 2D PAVs though a reversible C=C bond formation mechanism enabling precise crystallization control. This versatile approach affords robust 2D PAVs with honeycomb, square or kagome lattices, specific surface area up to ∼2,000 m 2 g −1 and lattice-mismatch tolerance up to 3.5%. High-resolution transmission electron microscopy and continuous rotation electron diffraction reveal molecular-level ordering in a 2-µm-sized triphenylbenzene-based single-crystalline 2D PAV. We demonstrate that crystallinity profoundly influences charge transport, with benzotrithiophene-based 2D PAVs exhibiting charge mobilities tenfold higher than their amorphous analogues or 2D polyimine precursors. This work establishes a general route to highly crystalline 2D conjugated polymer materials for robust applications.
Source: Nature Chemistry
Institutions: Center for Advancing Electronics Dresden, Technische Universität Dresden, Peking University, Beijing National Laboratory for Molecular Sciences, Universidad de Málaga, Universität Ulm, Fraunhofer Institute for Ceramic Technologies and Systems, Max Planck Institute for Polymer Research, Max Planck Institute of Microstructure Physics
Language: English
Subfield: Materials Chemistry
Field: Materials Science
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $12,690
Funders: Universidad de Málaga, Deutsche Forschungsgemeinschaft, National Natural Science Foundation of China, Max-Planck-Gesellschaft, Ministerio de Ciencia e Innovación, Peking University, Junta de Andalucía, Smithsonian Conservation Biology Institute, Agencia Estatal de Investigación, H2020 European Research Council
Awards: G1175115578, G1229826235, G1855990336, G2262748287, G2309174360, G2450367502, SFB 1415: Chemie der synthetischen zweidimensionalen Materialien, G2660406951, G300979063, G3480869486, G387506447, G425668148, G42699959, G430777504, G4369121744, G5080475149, G5421974903, G5662792045, G7084143925, Development of Thiophene Based Conjugated Polymers in Two Dimensions, G8920660035, G99296377
OpenAlex ID: W7124944101