{
  "abstract": "Force-adaptive polymer networks, whose mechanical response evolves under load, offer a route to structural materials that combine high stiffness and strength with efficient energy dissipation.[1,2] Most existing force-adaptive systems achieve this through mechanochemical reactions that generate reactive intermediates and thereby stiffen or rearrange the network,[3-5] a strategy that is intrinsically limited by diffusion, reaction kinetics, and the irreversible consumption of the reactive species. Here we pursue a fundamentally different strategy, in which a force-triggered transformation regulates the topological freedom of a slide-ring crosslink[6,7] rather than driving a chemical reaction. We integrate a mechanophore directly into the stopper of a rotaxane crosslinker, in which a cyclobutane formed by the [2+2] photodimerization of two cinnamate units[8,9] acts as the bulky stopper that confines a 24-crown-8 macrocycle on a dibenzylammonium axle.[10,11] Under load, retro-[2+2] cycloreversion reduces the steric dimension of the stopper and thereby expands the sliding space accessible to the macrocycle, so that a single covalent event gates a large slidingdissipation channel rather than dissipating energy directly. We incorporated this crosslinker into a segmented polyurethane and evaluated it against an orthogonal three-member sample set (R, C1, C2) of identical crosslinker content that decouples whether the stopper can open from whether the macrocycle can slide. The optimal composition, R3, reaches a toughness of about 215 MJ m-3 and a tensile strength of about 38 MPa—up to 9.4 and 5.6 times the toughness and strength of the openbut-cannot-slide control (C1), and far exceeding the constitutively sliding control (C2). Smallstrain dynamic mechanical analysis confirms that the mechanophore is silent at low strain, whereas gradient cyclic loading reveals a force-activation fingerprint: the dissipation ratio of R3 rises from below both controls at 100% strain to above them at high strain, crossing over near 300–400%. Infrared spectroscopy detects the regenerated cinnamate C=C band only after stretching and only in the cyclobutane-bearing samples,[8,9] and an annealing-reload test shows that the extra dissipation of R3 is largely recoverable with the smallest permanent damage of the three, consistent with a reversible sliding channel that shields the matrix.[12,13] These results establish a general design principle in which the structural precision of a mechanochemical transformation programs the evolution of topological freedom during deformation.",
  "abstract_shown": true,
  "affiliations": [],
  "article_type": null,
  "arxiv": null,
  "author_total": 2,
  "authors": [
    {
      "name": "Chenjuan Yu"
    },
    {
      "name": "Yuping Wang"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/6n625r7msjsk8.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15008824/v1",
  "fulltext_url": null,
  "id": "6n625r7msjsk8",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008824/v1",
  "language": null,
  "licence": "CC-BY-NC-ND",
  "licence_label": "CC BY-NC-ND",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by-nc-nd/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "2507|Polymer composites and self-healing"
    ]
  ],
  "openalex": "W7213332028",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15008824/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-14",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/6n625r7msjsk8.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:19Z",
      "native_id": "10.26434/chemrxiv.15008824",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008824/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:2507|Polymer composites and self-healing",
      "subfield": "materials-polymers"
    }
  ],
  "title": "Force-Programmed Evolution of Topological Freedom in Slide-Ring Polymer Networks",
  "title_text": "Force-Programmed Evolution of Topological Freedom in Slide-Ring Polymer Networks",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:19Z",
  "url": "https://research.draconitic.com/paper/6n625r7msjsk8",
  "venue": "ChemRxiv",
  "versions": []
}