{
  "abstract": "Intramolecular hydrogen-bonded networks have been designed and synthesized to control quinone redox thermodynamics in a family of anthraquinone (AQ) derivatives. The networks contain imidazole fused to AQ, which is hydrogen-bonded to the AQ carbonyl, and the extended motifs include phenol (P) and benzimidazole (BI). Cyclic voltammetry reveals a systematic anodic displacement of the AQ/AQ•- couple as the hydrogen-bonded network is extended, resulting in a cumulative +440 mV shift. Visible spectroelectrochemistry provides direct reduced-state markers: AQ exhibits AQ•- bands at ∼410 and ∼539 nm, whereas the intramolecular hydrogen-bonded constructs display only blue-shifted AQ•- signatures at ∼490 nm (BI-AQ), ∼505 nm (BIP-AQ), and ∼494 nm (BI2P-AQ), consistent with hydrogen-bond-dependent perturbation of the reduced quinone electronic structure. Infrared spectroelectrochemistry further resolves the underlying hydrogen-bonding interactions, revealing depletion of the neutral AQ ν(C═O) band (∼1667 cm-1) under reductive polarization with the emergence of hydrogen-bonded AQ•- band at ∼1480 cm-1 in the AQ derivatives. Oxidative polarization, yielding the phenoxyl radical, induces benzimidazolium formation and a blue-shifted AQ ν(C═O) band (∼1678 cm-1), highlighting the directional dependence of the perturbation and the role of the AQ carbonyl as a reporter of the interaction with the intramolecular hydrogen-bonded network. Treating the hydrogen-bonding protons quantum mechanically, nuclear-electronic orbital density functional theory calculations show strengthening of the hydrogen bonds cooperatively across the network upon one-electron reduction and oxidation, correctly predicting the observed stabilization of the AQ•- state. These fundamental insights will assist in the design of more precisely tuned catalysts.",
  "abstract_shown": true,
  "affiliations": [
    "School of Molecular Sciences, Arizona State University, Tempe, Arizona85287, United States.",
    "Department of Chemistry, Princeton University, Princeton, New Jersey08544, United States."
  ],
  "article_type": "research article",
  "arxiv": null,
  "author_total": 7,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Edwin J Gonzalez Lopez"
    },
    {
      "affs": [
        1
      ],
      "name": "Kai Cui",
      "orcid": "0000-0001-7311-1447"
    },
    {
      "affs": [
        1
      ],
      "name": "Jang Mok Yoo",
      "orcid": "0000-0002-3331-4909"
    },
    {
      "affs": [
        0
      ],
      "name": "Daniel A Heredia",
      "orcid": "0000-0002-0667-3906"
    },
    {
      "affs": [
        1
      ],
      "name": "Sharon Hammes-Schiffer",
      "orcid": "0000-0002-3782-6995"
    },
    {
      "affs": [
        0
      ],
      "name": "Thomas A Moore",
      "orcid": "0000-0002-1577-7117"
    },
    {
      "affs": [
        0
      ],
      "name": "Ana L Moore",
      "orcid": "0000-0002-6653-9506"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/2c9h4weswb3g9.bib",
  "cited_by": 0,
  "doi": "10.1021/jacs.6c15431",
  "fulltext_url": "https://europepmc.org/articles/PMC13632548",
  "id": "2c9h4weswb3g9",
  "issns": [
    "0002-7863",
    "1520-5126"
  ],
  "landing_url": "https://europepmc.org/article/MED/42937854",
  "language": "eng",
  "licence": "CC-BY-NC-ND",
  "licence_label": "CC BY-NC-ND",
  "licence_source": "article",
  "licence_url": "https://creativecommons.org/licenses/by-nc-nd/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "1606|Photochemistry and Electron Transfer Studies"
    ]
  ],
  "openalex": "W7213311997",
  "pdf_url": "https://europepmc.org/articles/PMC13632548?pdf=render",
  "pmcid": "PMC13632548",
  "pmid": "42937854",
  "published": "2026-09-01",
  "publisher": null,
  "ris": "https://research.draconitic.com/paper/2c9h4weswb3g9.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:22:24Z",
      "native_id": "MED:42937854",
      "source": "europepmc",
      "url": "https://europepmc.org/article/MED/42937854"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1606|Photochemistry and Electron Transfer Studies",
      "subfield": "physical"
    }
  ],
  "title": "Intramolecular Hydrogen-Bonded Networks for Tuning Anthraquinone Redox Properties.",
  "title_text": "Intramolecular Hydrogen-Bonded Networks for Tuning Anthraquinone Redox Properties.",
  "type": "peer-reviewed",
  "updated_at": "2026-10-30T12:22:24Z",
  "url": "https://research.draconitic.com/paper/2c9h4weswb3g9",
  "venue": "Journal of the American Chemical Society",
  "versions": []
}