{
  "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.",
  "abstract_shown": true,
  "affiliations": [
    "Laboratory for Functional Polymers, Swiss Federal Laboratories for Materials Science and Technology (Empa, Überlandstr. 129, Dübendorf, 8600",
    "Department of Materials, Swiss Federal Institute of Technology, ETH Zürich, Vladimir Prelog-Weg 5, Zürich, Switzerland, 8093",
    "Center for X-Ray Analytics, Swiss Federal Laboratories for Materials Science and Technology (Empa, Überlandstr. 129, Dübendorf, 8600",
    "Department of Chemistry, University of Fribourg, Chemin du Musée 9, Fribourg, Switzerland, 1700",
    "Building Energy Materials and Components, Swiss Federal Laboratories for Materials Science and Technology (Empa, Überlandstr. 129, Dübendorf, 8600",
    "Transport at Nanoscale Interfaces, Swiss Federal Laboratories for Materials Science and Technology (Empa, Überlandstr. 129, Dübendorf, 8600",
    "Laboratory for Nanomaterials in Health",
    "Swiss Federal Laboratories for Materials Science and Technology (Empa"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 7,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Valentin-Razvan Lupu"
    },
    {
      "affs": [
        2,
        3
      ],
      "name": "Antonia Neels"
    },
    {
      "affs": [
        4
      ],
      "name": "Paweł P. Ziemiański"
    },
    {
      "affs": [
        5
      ],
      "name": "Mirjana Dimitrievska"
    },
    {
      "affs": [
        6,
        7
      ],
      "name": "Vera Maria Kissling"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Dorina M. Opris"
    },
    {
      "name": "DORINA MARIA OPRIS",
      "orcid": "0000-0002-0585-7500"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/3p2zr08rh0vp2.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15009751/v1",
  "fulltext_url": null,
  "id": "3p2zr08rh0vp2",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009751/v1",
  "language": null,
  "licence": "CC-BY",
  "licence_label": "CC BY",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "2505|Covalent Organic Framework Applications"
    ]
  ],
  "openalex": "W7215100331",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15009751/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-01",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/3p2zr08rh0vp2.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:21Z",
      "native_id": "10.26434/chemrxiv.15009751",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009751/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:2505|Covalent Organic Framework Applications",
      "subfield": "materials-polymers"
    }
  ],
  "title": "Bulk Post-Polymerization Modification of a Single-Crystalline 2D Polymer via the Katritzky Reaction: A Modular Platform for Functional 2D Materials",
  "title_text": "Bulk Post-Polymerization Modification of a Single-Crystalline 2D Polymer via the Katritzky Reaction: A Modular Platform for Functional 2D Materials",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:21Z",
  "url": "https://research.draconitic.com/paper/3p2zr08rh0vp2",
  "venue": "ChemRxiv",
  "versions": []
}