{
  "abstract": "Molecular wires incorporating redox units are foundational to single-molecule electronics, yet the molecular designs and environment which govern whether charge-transport proceeds predominantly via phase-coherent quantum tunnelling or thermally activated incoherent hopping remains debated. By synthesising bench-stable Fe(III) ferrocenium wires ( ex-situ oxidation) and comparing their molecular conductance against electrochemically gated Fe(II) analogues ( in-situ oxidation) within scanning tunnelling microscopy break-junctions, we identify distinct experimental signatures of coexisting transport regimes. For both ferrocene and ferrocenium systems, while phase-coherent tunnelling through frontier molecular orbitals dominates at low bias, favourable environmental reorganisation energetics trigger efficient, two-step sequential processes at high biases. These findings resolve a long-standing mechanistic question in metallocene molecular electronics and highlight how two-terminal measurements alone are insufficient to resolve such ambiguities. Our combined electrochemical approach provides a pathway to more robust characterisation of transport phenomena in molecular junctions.",
  "abstract_shown": true,
  "affiliations": [
    "University of Liverpool",
    "University of Western Australia",
    "University of Warwick"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 15,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Linlin Hou"
    },
    {
      "affs": [
        1
      ],
      "name": "Varshini Kumar"
    },
    {
      "affs": [
        2
      ],
      "name": "Munirah Alsaqer"
    },
    {
      "affs": [
        0
      ],
      "name": "Amit Sil"
    },
    {
      "affs": [
        0
      ],
      "name": "James M. F. Morris"
    },
    {
      "affs": [
        0
      ],
      "name": "Chongguang Liu"
    },
    {
      "affs": [
        0
      ],
      "name": "Xiaohang Qiao"
    },
    {
      "affs": [
        0
      ],
      "name": "Adam Larbi"
    },
    {
      "affs": [
        2
      ],
      "name": "Abdalghani Daaoub"
    },
    {
      "affs": [
        1
      ],
      "name": "Stephen Moggach"
    },
    {
      "affs": [
        2
      ],
      "name": "Sara Sangtarash"
    },
    {
      "affs": [
        0
      ],
      "name": "Richard Nichols"
    },
    {
      "affs": [
        2
      ],
      "name": "Hatef Sadeghi"
    },
    {
      "affs": [
        1
      ],
      "name": "Paul Low"
    },
    {
      "affs": [
        0
      ],
      "name": "Andrea Vezzoli",
      "orcid": "0000-0002-8059-0113"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/72d473mzq8m2y.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv-2025-24d4d/v2",
  "fulltext_url": null,
  "id": "72d473mzq8m2y",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv-2025-24d4d/v2",
  "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",
      "2208|Molecular Junctions and Nanostructures"
    ]
  ],
  "openalex": "W7213884100",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv-2025-24d4d/v2",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-21",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/72d473mzq8m2y.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:19Z",
      "native_id": "10.26434/chemrxiv-2025-24d4d",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv-2025-24d4d/v2"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "source:chemrxiv",
      "subfield": "general"
    }
  ],
  "title": "Incoherent Transport Signatures in Ferrocene and Ferrocenium-based Molecular Wires",
  "title_text": "Incoherent Transport Signatures in Ferrocene and Ferrocenium-based Molecular Wires",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:19Z",
  "url": "https://research.draconitic.com/paper/72d473mzq8m2y",
  "venue": "ChemRxiv",
  "versions": []
}