{
  "abstract": "π-Multiradicalic compounds fabricated by on-surface synthesis have emerged as a powerful platform to interrogate spin interactions at the atomic scale. However, the introduction and role of unpaired d-electrons on such systems, and the study of π-d electronic interactions, are still incipient. In this context, a crucial point is the tunability of the inherent magnetic properties of such π-d architectures by incorporation of peripheral metal-organic coordination, which at the same time allows creating self-assembled architectures. Herein, to this aim we exploit an ex-professo synthesized Zn-porphyrin (1) equipped with two carbonitrile-dimethyl-phenyl moieties at its trans-meso positions, which forms π-extended metallo-organic nanostructures featuring unpaired π-electrons through cyclodehydrogenation and concomitant carbonitrile-gold coordination. Transmetallation of such Zn-based nanoarchitectures with Co atoms gave rise to the several Co-based porphyrin multiradicalic species featuring both unpaired π and d electrons, including porphyrin monomers (CoPor M) and dimers (Co-Por D) as well as one-dimensional porphyrin nanochains (1D CoPor NC) and nanotapes (1D CoPor NT). Scanning probe spectroscopy combined with theoretical calculations reveal that the carbonitrile-gold coordination environment dramatically alters the magnetic structure of the cobalt center as compared to analogue porphyrin species lacking the CN group. On the one hand, in both CoPor M and 1D CoPor NC the cobalt atom presents a S=3/2 ground state versus the S=1/2 case for Co porphyrins analogues lacking the nitrile moiety. Additionally, no Kondo interactions are detected at the metal center, as a consequence of a diminished magnetic interaction of CoPor M and 1D CoPor NC with the Au(111) substrate. On the other hand, CoPor D presents two radical electrons distributed between the cobalt atoms and the carbon π-system which interact ferromagnetically yielding a S=1 ground state. Our findings demonstrate how metal-ligand coordination can be used to harness the magnetic interactions within surface-supported multiradicalic molecular systems.",
  "abstract_shown": true,
  "affiliations": [
    "Instituto Madrileño de Estudios Avanzados en Nanociencia (IMDEA Nanoscience",
    "IMDEA Nanoscience",
    "Unidad asociada al CSIC por el ICMM",
    "Departamento de Química Orgánica",
    "Universidad Autónoma de Madrid",
    "Institute for Advanced Research in Chemical Sciences",
    "Universidad Autónoma de Madrid"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 15,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "María Tenorio"
    },
    {
      "affs": [
        0
      ],
      "name": "Lenka Cerna"
    },
    {
      "name": "Marco Lozano"
    },
    {
      "affs": [
        0,
        1,
        2
      ],
      "name": "Ana Barragán"
    },
    {
      "affs": [
        0
      ],
      "name": "Miguel Martínez García"
    },
    {
      "affs": [
        0
      ],
      "name": "Aurelio Gallardo"
    },
    {
      "affs": [
        0
      ],
      "name": "Koen Lauwaet"
    },
    {
      "affs": [
        0
      ],
      "name": "Shanmugasibi K. Mathialagan"
    },
    {
      "affs": [
        0
      ],
      "name": "Sofía O. Parreiras"
    },
    {
      "name": "José M. Gallego"
    },
    {
      "affs": [
        0,
        1,
        2
      ],
      "name": "José Ignacio Urgel"
    },
    {
      "affs": [
        0,
        3,
        4,
        5,
        6
      ],
      "name": "Tomás Torres"
    },
    {
      "affs": [
        0
      ],
      "name": "Diego Soler-Polo"
    },
    {
      "affs": [
        0,
        3,
        4,
        5,
        6
      ],
      "name": "Giovanni Bottari"
    },
    {
      "affs": [
        0,
        1,
        2
      ],
      "name": "David Écija"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/4dk4cab84cwyb.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15009863/v1",
  "fulltext_url": null,
  "id": "4dk4cab84cwyb",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009863/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",
      "2204|Surface Chemistry and Catalysis"
    ]
  ],
  "openalex": "W7220404256",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15009863/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-05",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/4dk4cab84cwyb.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:22Z",
      "native_id": "10.26434/chemrxiv.15009863",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009863/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "source:chemrxiv",
      "subfield": "general"
    }
  ],
  "title": "Harnessing π-d magnetic interactions in Co porphyrins by metal-ligand coordination",
  "title_text": "Harnessing π-d magnetic interactions in Co porphyrins by metal-ligand coordination",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:22Z",
  "url": "https://research.draconitic.com/paper/4dk4cab84cwyb",
  "venue": "ChemRxiv",
  "versions": []
}