{
  "abstract": "Molecular solar thermal (MOST) systems store solar energy in metastable photoisomers and release it on demand through triggered back-conversion. Here, we show that mixtures of MOST compounds enable a distinct energy-release strategy in which one component mediates the activation of another. Using methoxyphenyl-substituted norbornadiene/quadricyclane (NBD/QC) positional isomers, we show by in situ photoelectrochemical infrared reflection absorption spectroscopy (PEC-IRRAS) and density functional theory (DFT) that substituent position shifts the electrochemical onset potential by up to 0.6 V and controls switching selectivity, largely independently of thermal stability, a trend rationalized by calculated ionization potentials. Crucially, in a mixture, the electrochemically facile QC isomer triggers back-conversion of a second QC isomer below its intrinsic onset potential, consistent with a radical-chain mechanism. Mediator-assisted triggering thus decouples the requirements for molecular energy storage and electrochemical activation and opens new opportunities for tuning energy release strategies through multicomponent MOST systems.",
  "abstract_shown": true,
  "affiliations": [
    "Interface Research and Catalysis, Erlangen Center for Interface Research and Catalysis, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, Erlangen, Germany, 91058",
    "Interdisciplinary Center for Scientific Computing, Universität Heidelberg, Im Neuenheimer Feld 205 A, Heidelberg, Germany, 69120",
    "Institut Organische Chemie, Justus-Liebig-Universität Giessen, Heinrich-Buff-Ring 17, Gießen, Germany, 35392",
    "Department of Chemical Engineering, Universitat Politècnica de Catalunya, Eduard Maristany 10-14, Barcelona, Spain, 08019"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 7,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Zarah Hussain",
      "orcid": "0009-0003-8600-8934"
    },
    {
      "affs": [
        1
      ],
      "name": "Adrian J. Müller",
      "orcid": "0009-0008-8482-4790"
    },
    {
      "affs": [
        0
      ],
      "name": "Evanie Franz",
      "orcid": "0000-0002-2070-0050"
    },
    {
      "affs": [
        1
      ],
      "name": "Andreas Dreuw",
      "orcid": "0000-0002-5862-5113"
    },
    {
      "affs": [
        2,
        3
      ],
      "name": "Helen Hölzel",
      "orcid": "0000-0003-2312-9934"
    },
    {
      "affs": [
        0
      ],
      "name": "Olaf Brummel",
      "orcid": "0000-0001-5968-0774"
    },
    {
      "affs": [
        0
      ],
      "name": "Jörg Libuda",
      "orcid": "0000-0003-4713-5941"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/57e7kyj28ynb3.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15010832/v1",
  "fulltext_url": null,
  "id": "57e7kyj28ynb3",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010832/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",
      "1606|Chemical Reactions and Mechanisms"
    ]
  ],
  "openalex": "W7222358578",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15010832/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-22",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/57e7kyj28ynb3.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:24Z",
      "native_id": "10.26434/chemrxiv.15010832",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010832/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1606|Chemical Reactions and Mechanisms",
      "subfield": "physical"
    }
  ],
  "title": "Mediator-Assisted Energy Release Enabled by Positional Isomerism in Norbornadiene/Quadricyclane Systems",
  "title_text": "Mediator-Assisted Energy Release Enabled by Positional Isomerism in Norbornadiene/Quadricyclane Systems",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:24Z",
  "url": "https://research.draconitic.com/paper/57e7kyj28ynb3",
  "venue": "ChemRxiv",
  "versions": []
}