Control of Crystallinity of Vinylene-Linked Two-Dimensional Conjugated Polymers by Rational Monomer Design |
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| Authors: | Dominik L. Pastoetter Dr. Yannan Liu Dr. Matthew A. Addicoat Dr. Silvia Paasch Dr. Arezoo Dianat David Bodesheim Albrecht L. Waentig Dr. Shunqi Xu Mino Borrelli Dr. Alexander Croy Dr. Marcus Richter Prof. Dr. Eike Brunner Prof. Dr. Gianaurelio Cuniberti Prof. Dr. Xinliang Feng |
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| Affiliation: | 1. Chair of Molecular Functional Materials, Center for Advancing Electronics Dresden (cfaed) and Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01062 Dresden, Germany;2. School of Science and Technology, Nottingham Trent University Clifton Lane, Nottingham, NG118NS United Kingdom;3. Chair of Bioanalytical Chemistry, Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01062 Dresden, Germany;4. Chair of Material Science and Nanotechnology, Faculty of Mechanical Science and Engineering, Technische Universität Dresden, 01062 Dresden, Germany;5. Chair of Theoretical Chemistry Institute of Physical Chemistry, Friedrich Schiller University Jena, 07737 Jena, Germany |
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| Abstract: | The interest in two-dimensional conjugated polymers (2D CPs) has increased significantly in recent years. In particular, vinylene-linked 2D CPs with fully in-plane sp2-carbon-conjugated structures, high thermal and chemical stability, have become the focus of attention. Although the Horner-Wadsworth-Emmons (HWE) reaction has been recently demonstrated in synthesizing vinylene-linked 2D CPs, it remains largely unexplored due to the challenge in synthesis. In this work, we reveal the control of crystallinity of 2D CPs during the solvothermal synthesis of 2D-poly(phenylene-quinoxaline-vinylene)s (2D-PPQVs) and 2D-poly(phenylene-vinylene)s through the HWE polycondensation. The employment of fluorinated phosphonates and rigid aldehyde building blocks is demonstrated as crucial factors in enhancing the crystallinity of the obtained 2D CPs. Density functional theory (DFT) calculations reveal the critical role of the fluorinated phosphonate in enhancing the reversibility of the (semi)reversible C−C single bond formation. |
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| Keywords: | 2D covalent organic frameworks (2D COFs) 2D conjugated polymers Horner-Wadsworth-Emmons reaction sp2 carbon-conjugated vinylene- linked |
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