Bulk Post-Polymerization Modification of a Single-Crystalline 2D Polymer via the Katritzky Reaction: A Modular Platform for Functional 2D Materials
8 affiliations
- 1Laboratory for Functional Polymers, Swiss Federal Laboratories for Materials Science and Technology (Empa, Überlandstr. 129, Dübendorf, 8600
- 2Department of Materials, Swiss Federal Institute of Technology, ETH Zürich, Vladimir Prelog-Weg 5, Zürich, Switzerland, 8093
- 3Center for X-Ray Analytics, Swiss Federal Laboratories for Materials Science and Technology (Empa, Überlandstr. 129, Dübendorf, 8600
- 4Department of Chemistry, University of Fribourg, Chemin du Musée 9, Fribourg, Switzerland, 1700
- 5Building Energy Materials and Components, Swiss Federal Laboratories for Materials Science and Technology (Empa, Überlandstr. 129, Dübendorf, 8600
- 6Transport at Nanoscale Interfaces, Swiss Federal Laboratories for Materials Science and Technology (Empa, Überlandstr. 129, Dübendorf, 8600
- 7Laboratory for Nanomaterials in Health
- 8Swiss Federal Laboratories for Materials Science and Technology (Empa
Abstract
Synthesizing two-dimensional polymers (2DPs) via single-crystal-to-single-crystal (SCSC) topochemical polymerization presents a dual challenge: preorganizing multifunctional monomers into two-dimensional crystal lattices and ensuring their polymerizable groups remain in close proximity to enable topochemical reaction in 2D. Consequently, topochemical 2DPs remain rare, and strategies for their post-polymerization modification, a standard tool in 1D polymer chemistry, are even more limited. Existing pyrylium-functionalized 2DPs suffer from severe steric hindrance caused by 2,6-di-tert-butyl substituents on pyrylium, restricting their post-synthetic Katritzky transformations solely to small nucleophiles like ammonia. To overcome this limitation, we synthesized a 2,6-di(isopropyl)styrylpyrylium triolefin monomer featuring 2,6-di-isopropyl substituents on pyrylium instead of 2,6di-tert-butyl. This subtle steric modification preserves topochemical polymerizability, while dramatically enhancing the reactivity of the resulting 2DP, enabling facile pore-wall functionalization with nucleophiles such as methylamine or ethylenediamine, to form Nmethyl- and N-(2-aminoethyl)pyridinium sites, respectively. Spectroscopic measurements show no detectable residual pyrylium in either derivative, while the ion-exchange capacity of the N-methyl derivative agrees with its theoretical capacity. These results establish solid-state pyrylium-to-pyridinium conversion as a strategy for post-polymerization modification of a topochemical 2DP precursor and represent a solid foundation for accessing a wide variety of topochemical 2DPs with engineered pore functionality.
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BibTeX
@misc{lupu2026bulk,
title = {{Bulk Post-Polymerization Modification of a Single-Crystalline 2D Polymer via the Katritzky Reaction: A Modular Platform for Functional 2D Materials}},
author = {Valentin-Razvan Lupu and Antonia Neels and Paweł P. Ziemiański and Mirjana Dimitrievska and Vera Maria Kissling and Dorina M. Opris and DORINA MARIA OPRIS},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15009751/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009751/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Bulk Post-Polymerization Modification of a Single-Crystalline 2D Polymer via the Katritzky Reaction: A Modular Platform for Functional 2D Materials
AU - Valentin-Razvan Lupu
AU - Antonia Neels
AU - Paweł P. Ziemiański
AU - Mirjana Dimitrievska
AU - Vera Maria Kissling
AU - Dorina M. Opris
AU - DORINA MARIA OPRIS
PY - 2026
DA - 2026/10/01
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009751/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009751/v1
AB - Synthesizing two-dimensional polymers (2DPs) via single-crystal-to-single-crystal (SCSC) topochemical polymerization presents a dual challenge: preorganizing multifunctional monomers into two-dimensional crystal lattices and ensuring their polymerizable groups remain in close proximity to enable topochemical reaction in 2D. Consequently, topochemical 2DPs remain rare, and strategies for their post-polymerization modification, a standard tool in 1D polymer chemistry, are even more limited. Existing pyrylium-functionalized 2DPs suffer from severe steric hindrance caused by 2,6-di-tert-butyl substituents on pyrylium, restricting their post-synthetic Katritzky transformations solely to small nucleophiles like ammonia. To overcome this limitation, we synthesized a 2,6-di(isopropyl)styrylpyrylium triolefin monomer featuring 2,6-di-isopropyl substituents on pyrylium instead of 2,6di-tert-butyl. This subtle steric modification preserves topochemical polymerizability, while dramatically enhancing the reactivity of the resulting 2DP, enabling facile pore-wall functionalization with nucleophiles such as methylamine or ethylenediamine, to form Nmethyl- and N-(2-aminoethyl)pyridinium sites, respectively. Spectroscopic measurements show no detectable residual pyrylium in either derivative, while the ion-exchange capacity of the N-methyl derivative agrees with its theoretical capacity. These results establish solid-state pyrylium-to-pyridinium conversion as a strategy for post-polymerization modification of a topochemical 2DP precursor and represent a solid foundation for accessing a wide variety of topochemical 2DPs with engineered pore functionality.
ER -