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Combination of Knoevenagel Polycondensation and Water-Assisted Dynamic Michael-Addition-Elimination for the Synthesis of Vinylene-Linked 2D Covalent Organic Frameworks.
Xu, Shunqi; Liao, Zhongquan; Dianat, Arezoo; Park, Sang-Wook; Addicoat, Matthew A; Fu, Yubin; Pastoetter, Dominik L; Fabozzi, Filippo Giovanni; Liu, Yannan; Cuniberti, Gianaurelio; Richter, Marcus; Hecht, Stefan; Feng, Xinliang.
Afiliación
  • Xu S; Chair of Molecular Functional Materials, Center for Advancing Electronics Dresden (cfaed) and Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, Mommsenstrasse 4, 01069, Dresden, Germany.
  • Liao Z; Department of Synthetic Materials and Functional Devices, Max-Planck Institute of Microstructure Physics, 06120, Halle, Germany.
  • Dianat A; Fraunhofer Institute for Ceramic Technologies and Systems (IKTS), 01109, Dresden, Germany.
  • Park SW; Chair of Material Science and Nanotechnology, Faculty of Mechanical Science and Engineering, Technische Universität Dresden, Hallwachstraße 3, 01069, Dresden, Germany.
  • Addicoat MA; Chair of Molecular Functional Materials, Center for Advancing Electronics Dresden (cfaed) and Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, Mommsenstrasse 4, 01069, Dresden, Germany.
  • Fu Y; Leibniz-Institute for Polymer Research Dresden e.V. (IPF), 01069, Dresden, Germany.
  • Pastoetter DL; School of Science and Technology, Nottingham Trent University, Clifton Lane, Nottingham, NG11 8NS, UK.
  • Fabozzi FG; Chair of Molecular Functional Materials, Center for Advancing Electronics Dresden (cfaed) and Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, Mommsenstrasse 4, 01069, Dresden, Germany.
  • Liu Y; Chair of Molecular Functional Materials, Center for Advancing Electronics Dresden (cfaed) and Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, Mommsenstrasse 4, 01069, Dresden, Germany.
  • Cuniberti G; DWI-Leibniz Institute for Interactive Materials & Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, 52074, Aachen, Germany.
  • Richter M; Chair of Molecular Functional Materials, Center for Advancing Electronics Dresden (cfaed) and Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, Mommsenstrasse 4, 01069, Dresden, Germany.
  • Hecht S; Chair of Material Science and Nanotechnology, Faculty of Mechanical Science and Engineering, Technische Universität Dresden, Hallwachstraße 3, 01069, Dresden, Germany.
  • Feng X; Chair of Molecular Functional Materials, Center for Advancing Electronics Dresden (cfaed) and Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, Mommsenstrasse 4, 01069, Dresden, Germany.
Angew Chem Int Ed Engl ; 61(21): e202202492, 2022 May 16.
Article en En | MEDLINE | ID: mdl-35253336
Vinylene-linked two-dimensional conjugated covalent organic frameworks (V-2D-COFs), belonging to the class of two-dimensional conjugated polymers, have attracted increasing attention due to their extended π-conjugation over the 2D backbones associated with high chemical stability. The Knoevenagel polycondensation has been demonstrated as a robust synthetic method to provide cyano (CN)-substituted V-2D-COFs with unique optoelectronic, magnetic, and redox properties. Despite the successful synthesis, it remains elusive for the relevant polymerization mechanism, which leads to relatively low crystallinity and poor reproducibility. In this work, we demonstrate the novel synthesis of CN-substituted V-2D-COFs via the combination of Knoevenagel polycondensation and water-assisted dynamic Michael-addition-elimination, abbreviated as KMAE polymerization. The existence of C=C bond exchange between two diphenylacrylonitriles (M1 and M6) is firstly confirmed via in situ high-temperature NMR spectroscopy study of model reactions. Notably, the intermediate M4 synthesized via Michael-addition can proceed the Michael-elimination quantitatively, leading to an efficient C=C bond exchange, unambiguously confirming the dynamic nature of Michael-addition-elimination. Furthermore, the addition of water can significantly promote the reaction rate of Michael-addition-elimination for highly efficient C=C bond exchange within 5 mins. As a result, the KMAE polymerization provides a highly efficient strategy for the synthesis of CN-substituted V-2D-COFs with high crystallinity, as demonstrated by four examples of V-2D-COF-TFPB-PDAN, V-2D-COF-TFPT-PDAN, V-2D-COF-TFPB-BDAN, and V-2D-COF-HATN-BDAN, based on the simulated and experimental powder X-ray diffraction (PXRD) patterns as well as N2 -adsorption-desorption measurements. Moreover, high-resolution transmission electron microscopy (HR-TEM) analysis shows crystalline domain sizes ranging from 20 to 100 nm for the newly synthesized V-2D-COFs.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Angew Chem Int Ed Engl Año: 2022 Tipo del documento: Article País de afiliación: Alemania Pais de publicación: Alemania

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Angew Chem Int Ed Engl Año: 2022 Tipo del documento: Article País de afiliación: Alemania Pais de publicación: Alemania