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Nitrogen Enriched Trgers Base Polymers of Intrinsic Microporosity (TB-PIMs) for Heterogeneous Catalysis

Tash Hawkins, Ariana Antonangelo, MITCHELL WOOD, Elena Tocci, Johannes Carolus Jansen Orcid Logo, Alessio Fuoco Orcid Logo, Carmen Rizzuto, Mariagiulia Longo, Caterina Bezzu Orcid Logo, Mariolino Carta Orcid Logo

ACS Applied Polymer Materials, Volume: 7, Issue: 1, Pages: 220 - 233

Swansea University Authors: Tash Hawkins, Ariana Antonangelo, MITCHELL WOOD, Caterina Bezzu Orcid Logo, Mariolino Carta Orcid Logo

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DOI (Published version): 10.1021/acsapm.4c02952

Abstract

Heterogeneous catalysis is significantly enhanced by the use of highly porous polymers with specific functionalities, such as basic groups, which accelerate reaction rates. Polymers of intrinsic microporosity (PIMs) provide a unique platform for catalytic reactions owing to their high surface areas...

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Published in: ACS Applied Polymer Materials
ISSN: 2637-6105
Published: American Chemical Society (ACS) 2025
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URI: https://cronfa.swan.ac.uk/Record/cronfa68476
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Polymers of intrinsic microporosity (PIMs) provide a unique platform for catalytic reactions owing to their high surface areas and customizable pore structures. We herein report a series of Tr&#xF6;ger&#x2019;s base polymers (TB-PIMs) with enhanced basicity, achieved through the incorporation of nitrogen-containing groups into their repeat units, such as triazine and triphenylamine. These polymers offer a perfect balance between the pore &#x201C;swellability&#x201D;, which allows the use of substrates of various dimensions, and the basicity of their repeat units, which facilitates the use of reactants with diverse acidity. The catalytic activity is evaluated through the Knoevenagel condensation of benzaldehydes and various methylene species, conducted in the presence of ethanol as a green solvent and using a 1:1 ratio of the two reagents. The results highlight a significant improvement, with reactions reaching completion using just a 1% molar ratio of catalysts and achieving a 3-fold enhancement over previous results with 4-tert-butyl-benzaldehyde. Computational modeling confirms that the enhanced basicity of the repeat units is attributable to the polymer design. 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The authors kindly acknowledge Daniel M. Dawson and the University of St Andrews for the 13C SSNMR service. E.T., J.C.J., and A.F. received funding from the European Union&#x2019;s Horizon Europe research and innovation program under grant agreement no. 101115488, within the EIC pathfinder project &#x201C;DAM4CO2&#x201D;. 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spelling 2025-01-30T15:08:16.5803979 v2 68476 2024-12-06 Nitrogen Enriched Trgers Base Polymers of Intrinsic Microporosity (TB-PIMs) for Heterogeneous Catalysis 504b1b0b26830fee1373ecc50801f01a Tash Hawkins Tash Hawkins true false 4565af0854d884b5f995af8f5dc652fc Ariana Antonangelo Ariana Antonangelo true false df05265c2f51be338c248099bbc45101 MITCHELL WOOD MITCHELL WOOD true false 0ae638b129bf53b1ba5162afa9374e08 0000-0001-6918-8281 Caterina Bezzu Caterina Bezzu true false 56aebf2bba457f395149bbecbfa6d3eb 0000-0003-0718-6971 Mariolino Carta Mariolino Carta true false 2024-12-06 Heterogeneous catalysis is significantly enhanced by the use of highly porous polymers with specific functionalities, such as basic groups, which accelerate reaction rates. Polymers of intrinsic microporosity (PIMs) provide a unique platform for catalytic reactions owing to their high surface areas and customizable pore structures. We herein report a series of Tröger’s base polymers (TB-PIMs) with enhanced basicity, achieved through the incorporation of nitrogen-containing groups into their repeat units, such as triazine and triphenylamine. These polymers offer a perfect balance between the pore “swellability”, which allows the use of substrates of various dimensions, and the basicity of their repeat units, which facilitates the use of reactants with diverse acidity. The catalytic activity is evaluated through the Knoevenagel condensation of benzaldehydes and various methylene species, conducted in the presence of ethanol as a green solvent and using a 1:1 ratio of the two reagents. The results highlight a significant improvement, with reactions reaching completion using just a 1% molar ratio of catalysts and achieving a 3-fold enhancement over previous results with 4-tert-butyl-benzaldehyde. Computational modeling confirms that the enhanced basicity of the repeat units is attributable to the polymer design. Additionally, preliminary studies are undertaken to assess the kinetics of the catalyzed condensation reaction. Journal Article ACS Applied Polymer Materials 7 1 220 233 American Chemical Society (ACS) 2637-6105 Heterogeneous catalysis; Tröger’s base; PIMs; Knoevenagel; microporosity 10 1 2025 2025-01-10 10.1021/acsapm.4c02952 COLLEGE NANME COLLEGE CODE Swansea University SU Library paid the OA fee (TA Institutional Deal) M.C., A.R.A., and N.H. gratefully acknowledge funding from the Engineering and Physical Sciences Research Council (EPSRC), Grant number: EP/T007362/1 “Novel polymers of intrinsic microporosity for heterogeneous base-catalysed reactions (HBC-PIMs)” and Swansea University. The authors kindly acknowledge Daniel M. Dawson and the University of St Andrews for the 13C SSNMR service. E.T., J.C.J., and A.F. received funding from the European Union’s Horizon Europe research and innovation program under grant agreement no. 101115488, within the EIC pathfinder project “DAM4CO2”. M.C., E.T., J.C.J., A.F., and C.G.B. also thank the Royal Society for the bilateral grant IEC\R2\222044. 2025-01-30T15:08:16.5803979 2024-12-06T10:39:00.7201201 Faculty of Science and Engineering School of Engineering and Applied Sciences - Chemistry Tash Hawkins 1 Ariana Antonangelo 2 MITCHELL WOOD 3 Elena Tocci 4 Johannes Carolus Jansen 0000-0003-4538-6851 5 Alessio Fuoco orcid.org/0000-0003-4538-6851 6 Carmen Rizzuto 7 Mariagiulia Longo 8 Caterina Bezzu 0000-0001-6918-8281 9 Mariolino Carta 0000-0003-0718-6971 10 68476__33445__622cb2f61dc3414195e783c71baf43c8.pdf 68476.VOR.pdf 2025-01-30T14:54:15.3406992 Output 10533142 application/pdf Version of Record true © 2024 The Authors. This publication is licensed under CC-BY 4.0. true eng https://creativecommons.org/licenses/by/4.0/
title Nitrogen Enriched Trgers Base Polymers of Intrinsic Microporosity (TB-PIMs) for Heterogeneous Catalysis
spellingShingle Nitrogen Enriched Trgers Base Polymers of Intrinsic Microporosity (TB-PIMs) for Heterogeneous Catalysis
Tash Hawkins
Ariana Antonangelo
MITCHELL WOOD
Caterina Bezzu
Mariolino Carta
title_short Nitrogen Enriched Trgers Base Polymers of Intrinsic Microporosity (TB-PIMs) for Heterogeneous Catalysis
title_full Nitrogen Enriched Trgers Base Polymers of Intrinsic Microporosity (TB-PIMs) for Heterogeneous Catalysis
title_fullStr Nitrogen Enriched Trgers Base Polymers of Intrinsic Microporosity (TB-PIMs) for Heterogeneous Catalysis
title_full_unstemmed Nitrogen Enriched Trgers Base Polymers of Intrinsic Microporosity (TB-PIMs) for Heterogeneous Catalysis
title_sort Nitrogen Enriched Trgers Base Polymers of Intrinsic Microporosity (TB-PIMs) for Heterogeneous Catalysis
author_id_str_mv 504b1b0b26830fee1373ecc50801f01a
4565af0854d884b5f995af8f5dc652fc
df05265c2f51be338c248099bbc45101
0ae638b129bf53b1ba5162afa9374e08
56aebf2bba457f395149bbecbfa6d3eb
author_id_fullname_str_mv 504b1b0b26830fee1373ecc50801f01a_***_Tash Hawkins
4565af0854d884b5f995af8f5dc652fc_***_Ariana Antonangelo
df05265c2f51be338c248099bbc45101_***_MITCHELL WOOD
0ae638b129bf53b1ba5162afa9374e08_***_Caterina Bezzu
56aebf2bba457f395149bbecbfa6d3eb_***_Mariolino Carta
author Tash Hawkins
Ariana Antonangelo
MITCHELL WOOD
Caterina Bezzu
Mariolino Carta
author2 Tash Hawkins
Ariana Antonangelo
MITCHELL WOOD
Elena Tocci
Johannes Carolus Jansen
Alessio Fuoco
Carmen Rizzuto
Mariagiulia Longo
Caterina Bezzu
Mariolino Carta
format Journal article
container_title ACS Applied Polymer Materials
container_volume 7
container_issue 1
container_start_page 220
publishDate 2025
institution Swansea University
issn 2637-6105
doi_str_mv 10.1021/acsapm.4c02952
publisher American Chemical Society (ACS)
college_str Faculty of Science and Engineering
hierarchytype
hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Chemistry{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Chemistry
document_store_str 1
active_str 0
description Heterogeneous catalysis is significantly enhanced by the use of highly porous polymers with specific functionalities, such as basic groups, which accelerate reaction rates. Polymers of intrinsic microporosity (PIMs) provide a unique platform for catalytic reactions owing to their high surface areas and customizable pore structures. We herein report a series of Tröger’s base polymers (TB-PIMs) with enhanced basicity, achieved through the incorporation of nitrogen-containing groups into their repeat units, such as triazine and triphenylamine. These polymers offer a perfect balance between the pore “swellability”, which allows the use of substrates of various dimensions, and the basicity of their repeat units, which facilitates the use of reactants with diverse acidity. The catalytic activity is evaluated through the Knoevenagel condensation of benzaldehydes and various methylene species, conducted in the presence of ethanol as a green solvent and using a 1:1 ratio of the two reagents. The results highlight a significant improvement, with reactions reaching completion using just a 1% molar ratio of catalysts and achieving a 3-fold enhancement over previous results with 4-tert-butyl-benzaldehyde. Computational modeling confirms that the enhanced basicity of the repeat units is attributable to the polymer design. Additionally, preliminary studies are undertaken to assess the kinetics of the catalyzed condensation reaction.
published_date 2025-01-10T09:30:52Z
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score 11.055693

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