{
  "abstract": "Reactions between ions of identical polarity are usually prevented by a strong Coulomb barrier in the gas phase. Here, we systematically investigate the binding of gaseous reactive anions to anions at a vacuum layer interface and develop our findings into a method for the controlled build-up of highly charged molecular anions and nanoclusters. Following a previous observation of dimeric ions in trace amounts upon the mass-selective deposition of the reactive fragment anion [B 12 I 11 ] – , the procedure was optimized here to oligomerize such ions, resulting in highly charged anionic chains. The surface products were detected using electrospray mass spectrometry after their dissolution. Experimental and computational investigations show that the isolated multiply charged ions are metastable against charge-separating fragmentation. Sequential deposition of two distinct reactive anions enables the formation of mixed oligomers. The deposition sequence and ion-beam focus can control the interfacial reaction, thereby enabling the selective generation of constitutional isomers. To generate stable anions with high negative charge states, ions featuring a positive center for Coulomb stabilization and multiple interface-active organic groups for anion binding were deposited sequentially with reactive anions. Stable products with a negative charge state of –7 were detected as free gaseous anions, surpassing the known limits of negative charge states of similarly sized ions. Finally, we demonstrate that this concept of targeted anion-anion reactions at interfaces can be extended to other functional ions, paving the way for a broadly applicable approach to interface design with charged building blocks and, therefore, offering potential applications in charge-state-based multilevel memory nodes, electrode functionalization, and photonics. Furthermore, the generated products provide fundamental insights into excess charge stabilization in nanosized units and reactivity in highly charged environments.",
  "abstract_shown": true,
  "affiliations": [
    "Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Linnéstr. 2, Leipzig, Germany, 04103",
    "Institut für Organische Chemie, Universität Leipzig, Johannisallee 29, Leipzig, Germany, D-04103",
    "Leibniz Institut für Oberflächenmodifizierung (IOM), Permoserstraße 15, Leipzig, Germany, 04318"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 8,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Kay Antonio Behrend",
      "orcid": "0009-0007-1991-0089"
    },
    {
      "affs": [
        0
      ],
      "name": "Markus Rohdenburg",
      "orcid": "0000-0001-8533-3610"
    },
    {
      "affs": [
        0
      ],
      "name": "Pia K. Schäferjohann",
      "orcid": "0009-0005-2586-4037"
    },
    {
      "affs": [
        0
      ],
      "name": "Harald Knorke",
      "orcid": "0000-0001-6070-1827"
    },
    {
      "affs": [
        0
      ],
      "name": "Aby-Paul Benny",
      "orcid": "0009-0002-5258-2500"
    },
    {
      "affs": [
        1
      ],
      "name": "Tillmann G. Fischer",
      "orcid": "0000-0003-4480-8661"
    },
    {
      "affs": [
        1
      ],
      "name": "Kirsten Zeitler",
      "orcid": "0000-0003-1549-5002"
    },
    {
      "affs": [
        0,
        2
      ],
      "name": "Jonas Warneke",
      "orcid": "0000-0002-3233-7412"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/00mrt3j4cnk0e.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15009376/v1",
  "fulltext_url": null,
  "id": "00mrt3j4cnk0e",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009376/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",
      "1607|Mass Spectrometry Techniques and Applications"
    ]
  ],
  "openalex": "W7214071052",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15009376/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-23",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/00mrt3j4cnk0e.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:21Z",
      "native_id": "10.26434/chemrxiv.15009376",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009376/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1607|Mass Spectrometry Techniques and Applications",
      "subfield": "physical"
    }
  ],
  "title": "Controlled Buildup of Multiply Charged Anionic Clusters at Interfaces Using Anion-Anion Reactions",
  "title_text": "Controlled Buildup of Multiply Charged Anionic Clusters at Interfaces Using Anion-Anion Reactions",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:21Z",
  "url": "https://research.draconitic.com/paper/00mrt3j4cnk0e",
  "venue": "ChemRxiv",
  "versions": []
}