Vinylene-Linked 2D Conjugated Covalent Organic Frameworks by Wittig Reactions

Yannan Liu; Shuai Fu; Dominik L. Pastoetter; Arafat Hossain Khan; Yingying Zhang; Arezoo Dianat; Shunqi Xu; Zhongquan Liao; Marcus Richter; Minghao Yu; Miroslav Položij; Eike Brunner; Gianaurelio Cuniberti; Thomas Heine; Mischa Bonn; Hai I. Wang; Xinliang Feng

doi:10.1002/anie.202209762

Vinylene-Linked 2D Conjugated Covalent Organic Frameworks by Wittig Reactions

Yannan Liu, Shuai Fu, Dominik L. Pastoetter, Arafat Hossain Khan, Yingying Zhang, Arezoo Dianat, Shunqi Xu, Zhongquan Liao, Marcus Richter, Minghao Yu, Miroslav Položij, Eike Brunner, Gianaurelio Cuniberti, Thomas Heine, Mischa Bonn, Hai I. Wang, Xinliang Feng

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Vinylene-linked two-dimensional covalent organic frameworks (V-2D-COFs) have shown great promise in electronics and optoelectronics. However, only a few reactions for V-2D-COFs have been developed hitherto. Besides the kinetically low reversibility of C=C bond formation, another underlying issue facing the synthesis of V-2D-COFs is the attainment of high (E)-alkene selectivity to ensure the appropriate symmetry of 2D frameworks. Here, we tailor the E/Z selectivity of the Wittig reaction by employing a proper catalyst (i.e., Cs₂CO₃) to obtain more stable intermediates and elevating the temperature across the reaction barrier. Subsequently, the Wittig reaction is innovatively utilized for the synthesis of four crystalline V-2D-COFs by combining aldehydes and ylides. Importantly, the efficient conjugation and decent crystallinity of the resultant V-2D-COFs are demonstrated by their high charge carrier mobilities over 10 cm² V⁻¹ s⁻¹, as revealed by non-contact terahertz (THz) spectroscopy.

Original language	English
Article number	e202209762
Journal	Angewandte Chemie - International Edition
Volume	61
Issue number	49
DOIs	https://doi.org/10.1002/anie.202209762
Publication status	Published - 2022 Dec 5

Bibliographical note

Funding Information:
We thank the financial support from European Union's Horizon 2020 research and innovation programme (GrapheneCore3 881603), M‐ERA.NET and Sächsisches Staatsministerium für Wissenschaft und Kunst (HYSUCAP 100478697 & Sonderzuweisung zur Unterstützung profilbestimmender Struktureinheiten), the ERC Consolidator Grant (T2DCP, NO. 819698), the DFG for the CRC 1415 (No. 417590517), Polymer‐based Batteries (SPP 2248, RACOF‐MMIS) and H2020‐MSCA‐ITN (ULTIMATE, No. 813036). S.F. and Y.Z. acknowledges fellowship support from the China Scholarship Council (CSC). We thank Dr. Guangbo Chen (TU Dresden) for the BET measurements and Dr. Zhiyong Wang (TU Dresden) for the TEM measurements. We thank Dr. Mingchao Wang for the helpful discussion. The author also acknowledges the Centre for Information Services and High Performance Computing (ZIH) in Dresden, Germany, for the provided computational resources. Open Access funding enabled and organized by Projekt DEAL.

Funding Information:
We thank the financial support from European Union's Horizon 2020 research and innovation programme (GrapheneCore3 881603), M-ERA.NET and Sächsisches Staatsministerium für Wissenschaft und Kunst (HYSUCAP 100478697 & Sonderzuweisung zur Unterstützung profilbestimmender Struktureinheiten), the ERC Consolidator Grant (T2DCP, NO. 819698), the DFG for the CRC 1415 (No. 417590517), Polymer-based Batteries (SPP 2248, RACOF-MMIS) and H2020-MSCA-ITN (ULTIMATE, No. 813036). S.F. and Y.Z. acknowledges fellowship support from the China Scholarship Council (CSC). We thank Dr. Guangbo Chen (TU Dresden) for the BET measurements and Dr. Zhiyong Wang (TU Dresden) for the TEM measurements. We thank Dr. Mingchao Wang for the helpful discussion. The author also acknowledges the Centre for Information Services and High Performance Computing (ZIH) in Dresden, Germany, for the provided computational resources. Open Access funding enabled and organized by Projekt DEAL.

Publisher Copyright:
© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)

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10.1002/anie.202209762

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Liu, Y., Fu, S., Pastoetter, D. L., Khan, A. H., Zhang, Y., Dianat, A., Xu, S., Liao, Z., Richter, M., Yu, M., Položij, M., Brunner, E., Cuniberti, G., Heine, T., Bonn, M., Wang, H. I., & Feng, X. (2022). Vinylene-Linked 2D Conjugated Covalent Organic Frameworks by Wittig Reactions. Angewandte Chemie - International Edition, 61(49), [e202209762]. https://doi.org/10.1002/anie.202209762

@article{13947e3ef07f42e3b72cfa0b94cb5ec7,

title = "Vinylene-Linked 2D Conjugated Covalent Organic Frameworks by Wittig Reactions",

abstract = "Vinylene-linked two-dimensional covalent organic frameworks (V-2D-COFs) have shown great promise in electronics and optoelectronics. However, only a few reactions for V-2D-COFs have been developed hitherto. Besides the kinetically low reversibility of C=C bond formation, another underlying issue facing the synthesis of V-2D-COFs is the attainment of high (E)-alkene selectivity to ensure the appropriate symmetry of 2D frameworks. Here, we tailor the E/Z selectivity of the Wittig reaction by employing a proper catalyst (i.e., Cs2CO3) to obtain more stable intermediates and elevating the temperature across the reaction barrier. Subsequently, the Wittig reaction is innovatively utilized for the synthesis of four crystalline V-2D-COFs by combining aldehydes and ylides. Importantly, the efficient conjugation and decent crystallinity of the resultant V-2D-COFs are demonstrated by their high charge carrier mobilities over 10 cm2 V−1 s−1, as revealed by non-contact terahertz (THz) spectroscopy.",

author = "Yannan Liu and Shuai Fu and Pastoetter, {Dominik L.} and Khan, {Arafat Hossain} and Yingying Zhang and Arezoo Dianat and Shunqi Xu and Zhongquan Liao and Marcus Richter and Minghao Yu and Miroslav Polo{\v z}ij and Eike Brunner and Gianaurelio Cuniberti and Thomas Heine and Mischa Bonn and Wang, {Hai I.} and Xinliang Feng",

note = "Funding Information: We thank the financial support from European Union's Horizon 2020 research and innovation programme (GrapheneCore3 881603), M‐ERA.NET and S{\"a}chsisches Staatsministerium f{\"u}r Wissenschaft und Kunst (HYSUCAP 100478697 & Sonderzuweisung zur Unterst{\"u}tzung profilbestimmender Struktureinheiten), the ERC Consolidator Grant (T2DCP, NO. 819698), the DFG for the CRC 1415 (No. 417590517), Polymer‐based Batteries (SPP 2248, RACOF‐MMIS) and H2020‐MSCA‐ITN (ULTIMATE, No. 813036). S.F. and Y.Z. acknowledges fellowship support from the China Scholarship Council (CSC). We thank Dr. Guangbo Chen (TU Dresden) for the BET measurements and Dr. Zhiyong Wang (TU Dresden) for the TEM measurements. We thank Dr. Mingchao Wang for the helpful discussion. The author also acknowledges the Centre for Information Services and High Performance Computing (ZIH) in Dresden, Germany, for the provided computational resources. Open Access funding enabled and organized by Projekt DEAL. Funding Information: We thank the financial support from European Union's Horizon 2020 research and innovation programme (GrapheneCore3 881603), M-ERA.NET and S{\"a}chsisches Staatsministerium f{\"u}r Wissenschaft und Kunst (HYSUCAP 100478697 & Sonderzuweisung zur Unterst{\"u}tzung profilbestimmender Struktureinheiten), the ERC Consolidator Grant (T2DCP, NO. 819698), the DFG for the CRC 1415 (No. 417590517), Polymer-based Batteries (SPP 2248, RACOF-MMIS) and H2020-MSCA-ITN (ULTIMATE, No. 813036). S.F. and Y.Z. acknowledges fellowship support from the China Scholarship Council (CSC). We thank Dr. Guangbo Chen (TU Dresden) for the BET measurements and Dr. Zhiyong Wang (TU Dresden) for the TEM measurements. We thank Dr. Mingchao Wang for the helpful discussion. The author also acknowledges the Centre for Information Services and High Performance Computing (ZIH) in Dresden, Germany, for the provided computational resources. Open Access funding enabled and organized by Projekt DEAL. Publisher Copyright: {\textcopyright} 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.",

year = "2022",

month = dec,

day = "5",

doi = "10.1002/anie.202209762",

language = "English",

volume = "61",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

number = "49",

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Liu, Y, Fu, S, Pastoetter, DL, Khan, AH, Zhang, Y, Dianat, A, Xu, S, Liao, Z, Richter, M, Yu, M, Položij, M, Brunner, E, Cuniberti, G, Heine, T, Bonn, M, Wang, HI & Feng, X 2022, 'Vinylene-Linked 2D Conjugated Covalent Organic Frameworks by Wittig Reactions', Angewandte Chemie - International Edition, vol. 61, no. 49, e202209762. https://doi.org/10.1002/anie.202209762

TY - JOUR

T1 - Vinylene-Linked 2D Conjugated Covalent Organic Frameworks by Wittig Reactions

AU - Liu, Yannan

AU - Fu, Shuai

AU - Pastoetter, Dominik L.

AU - Khan, Arafat Hossain

AU - Zhang, Yingying

AU - Dianat, Arezoo

AU - Xu, Shunqi

AU - Liao, Zhongquan

AU - Richter, Marcus

AU - Yu, Minghao

AU - Položij, Miroslav

AU - Brunner, Eike

AU - Cuniberti, Gianaurelio

AU - Heine, Thomas

AU - Bonn, Mischa

AU - Wang, Hai I.

AU - Feng, Xinliang

N1 - Funding Information: We thank the financial support from European Union's Horizon 2020 research and innovation programme (GrapheneCore3 881603), M‐ERA.NET and Sächsisches Staatsministerium für Wissenschaft und Kunst (HYSUCAP 100478697 & Sonderzuweisung zur Unterstützung profilbestimmender Struktureinheiten), the ERC Consolidator Grant (T2DCP, NO. 819698), the DFG for the CRC 1415 (No. 417590517), Polymer‐based Batteries (SPP 2248, RACOF‐MMIS) and H2020‐MSCA‐ITN (ULTIMATE, No. 813036). S.F. and Y.Z. acknowledges fellowship support from the China Scholarship Council (CSC). We thank Dr. Guangbo Chen (TU Dresden) for the BET measurements and Dr. Zhiyong Wang (TU Dresden) for the TEM measurements. We thank Dr. Mingchao Wang for the helpful discussion. The author also acknowledges the Centre for Information Services and High Performance Computing (ZIH) in Dresden, Germany, for the provided computational resources. Open Access funding enabled and organized by Projekt DEAL. Funding Information: We thank the financial support from European Union's Horizon 2020 research and innovation programme (GrapheneCore3 881603), M-ERA.NET and Sächsisches Staatsministerium für Wissenschaft und Kunst (HYSUCAP 100478697 & Sonderzuweisung zur Unterstützung profilbestimmender Struktureinheiten), the ERC Consolidator Grant (T2DCP, NO. 819698), the DFG for the CRC 1415 (No. 417590517), Polymer-based Batteries (SPP 2248, RACOF-MMIS) and H2020-MSCA-ITN (ULTIMATE, No. 813036). S.F. and Y.Z. acknowledges fellowship support from the China Scholarship Council (CSC). We thank Dr. Guangbo Chen (TU Dresden) for the BET measurements and Dr. Zhiyong Wang (TU Dresden) for the TEM measurements. We thank Dr. Mingchao Wang for the helpful discussion. The author also acknowledges the Centre for Information Services and High Performance Computing (ZIH) in Dresden, Germany, for the provided computational resources. Open Access funding enabled and organized by Projekt DEAL. Publisher Copyright: © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

PY - 2022/12/5

Y1 - 2022/12/5

N2 - Vinylene-linked two-dimensional covalent organic frameworks (V-2D-COFs) have shown great promise in electronics and optoelectronics. However, only a few reactions for V-2D-COFs have been developed hitherto. Besides the kinetically low reversibility of C=C bond formation, another underlying issue facing the synthesis of V-2D-COFs is the attainment of high (E)-alkene selectivity to ensure the appropriate symmetry of 2D frameworks. Here, we tailor the E/Z selectivity of the Wittig reaction by employing a proper catalyst (i.e., Cs2CO3) to obtain more stable intermediates and elevating the temperature across the reaction barrier. Subsequently, the Wittig reaction is innovatively utilized for the synthesis of four crystalline V-2D-COFs by combining aldehydes and ylides. Importantly, the efficient conjugation and decent crystallinity of the resultant V-2D-COFs are demonstrated by their high charge carrier mobilities over 10 cm2 V−1 s−1, as revealed by non-contact terahertz (THz) spectroscopy.

AB - Vinylene-linked two-dimensional covalent organic frameworks (V-2D-COFs) have shown great promise in electronics and optoelectronics. However, only a few reactions for V-2D-COFs have been developed hitherto. Besides the kinetically low reversibility of C=C bond formation, another underlying issue facing the synthesis of V-2D-COFs is the attainment of high (E)-alkene selectivity to ensure the appropriate symmetry of 2D frameworks. Here, we tailor the E/Z selectivity of the Wittig reaction by employing a proper catalyst (i.e., Cs2CO3) to obtain more stable intermediates and elevating the temperature across the reaction barrier. Subsequently, the Wittig reaction is innovatively utilized for the synthesis of four crystalline V-2D-COFs by combining aldehydes and ylides. Importantly, the efficient conjugation and decent crystallinity of the resultant V-2D-COFs are demonstrated by their high charge carrier mobilities over 10 cm2 V−1 s−1, as revealed by non-contact terahertz (THz) spectroscopy.

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JO - Angewandte Chemie - International Edition

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ER -

Vinylene-Linked 2D Conjugated Covalent Organic Frameworks by Wittig Reactions

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