{
  "abstract": "Precise control over the nuclearity and spatial organization of metal ions is a central objective in coordination chemistry. Knotting imposes severe geometric constraints on frameworks but has rarely been exploited to organize inequivalent metal-binding sites within a single ligand. Here we report that a molecular cinquefoil knot containing both bidentate and tridentate chelating sites enables programmed metal-ion coordination pathways. Direct metalation affords Mn(II)5-, Fe(II)5-, Co(II)5-, and Cd(II)5-knots through a dinuclear intermediate and an unusual 2-to-5 metal nuclearity progression, even though these metals do not template knot formation. Crystallization of a Mn(II)2-intermediate reveals partial demetalation but retains a Mn(II) center displaying a “3 + 3” coordination mode, whereas all Fe(II) ions in the fully metalated Fe(II)5-knot adopt a “3 + 2” binding geometry. Together with computational simulations, these observations support a stepwise metalation mechanism in which the dinuclear “3 + 3” coordination environment evolves into the “3 + 2” motif of the pentanuclear knot. Although the Ni(II)5- knot cannot be obtained by direct metalation because of slow incorporation, it forms readily via transmetalation from a Zn(II)5-knot. Circular dichroism measurements show that chiral expression is dictated by the overall ligand arrangement rather than the identity of the metal ions. The work demonstrates molecular knotting as a strategy for pathway-controlled multi-metallic assembly.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Chemistry, Fudan University, Shanghai 200438, People’s Republic of China",
    "State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, University of Chinese Academy of Sciences, Shanghai 200032, People’s Republic of China",
    "State Key Laboratory of Molecular Engineering of Polymers and Department of Macromolecular Science, Fudan University, Shanghai 200433, People’s Republic of China",
    "School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, People’s Republic of China"
  ],
  "article_type": "research article",
  "arxiv": null,
  "author_total": 7,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Guanyu Chi"
    },
    {
      "affs": [
        1
      ],
      "name": "Bo Li"
    },
    {
      "affs": [
        2
      ],
      "name": "Hai-Na Feng"
    },
    {
      "affs": [
        3
      ],
      "name": "Zhi-Hui Zhang"
    },
    {
      "affs": [
        1
      ],
      "name": "Heng Wang",
      "orcid": "0000-0002-6829-7205"
    },
    {
      "affs": [
        1
      ],
      "name": "Xiaopeng Li",
      "orcid": "0000-0001-9655-9551"
    },
    {
      "affs": [
        0
      ],
      "name": "Liang Zhang",
      "orcid": "0000-0001-8605-8681"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/2vtn4p3rabcdc.bib",
  "cited_by": 0,
  "doi": "10.1073/pnas.2610851123",
  "fulltext_url": "https://pmc.ncbi.nlm.nih.gov/articles/PMC13732044/",
  "id": "2vtn4p3rabcdc",
  "issns": [
    "0027-8424",
    "1091-6490"
  ],
  "landing_url": "https://doi.org/10.1073/pnas.2610851123",
  "language": "en",
  "licence": "CC-BY-NC-ND-4.0",
  "licence_label": "CC BY-NC-ND 4.0",
  "licence_source": "article",
  "licence_url": "https://creativecommons.org/licenses/by-nc-nd/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "heading",
      "410"
    ],
    [
      "heading",
      "Chemistry"
    ],
    [
      "heading",
      "Physical Sciences"
    ],
    [
      "openalex",
      "1605|Supramolecular Chemistry and Complexes"
    ]
  ],
  "openalex": "W7223973984",
  "pdf_url": null,
  "pmcid": "PMC13732044",
  "pmid": "42945258",
  "published": "2026-10-27",
  "publisher": "National Academy of Sciences",
  "ris": "https://research.draconitic.com/paper/2vtn4p3rabcdc.ris",
  "sources": [
    {
      "first_seen": "2026-11-08T12:22:06Z",
      "native_id": "PMC13732044",
      "source": "pmc",
      "url": "https://doi.org/10.1073/pnas.2610851123"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Supramolecular Chemistry and Complexes",
      "subfield": "organic"
    }
  ],
  "title": "Encoding metal coordination pathways and nuclearity by molecular knotting",
  "title_text": "Encoding metal coordination pathways and nuclearity by molecular knotting",
  "type": "peer-reviewed",
  "updated_at": "2026-11-08T12:22:06Z",
  "url": "https://research.draconitic.com/paper/2vtn4p3rabcdc",
  "venue": "Proceedings of the National Academy of Sciences of the United States of America",
  "versions": []
}