{
  "abstract": "Layered Ruddlesden–Popper (RP) oxides provide a versatile platform for topochemical anion modification, enabling access to metastable mixed-anion phases with tuneable structural and electronic properties. In this work, we present a comprehensive investigation of how mixed B -site (indium and antimony) chemistry influences topochemical fluorination of Ba 2 In 0.5 Sb 0.5 O 4 using polyvinylidene fluoride (PVDF). Powder X-ray diffraction (PXRD) reveals anisotropic lattice expansion, dominated by elongation perpendicular to the perovskite layers, with minimal change in the in-plane lattice parameters. Fluorination proceeds through a composition-dependent multiphase regime in which several tetragonal ( I 4 /mmm ) RP components with progressively expanded c and slightly contracted a lattice parameters coexist, representing a distribution of fluorination states, followed by convergence to a single dominant fluorine-rich tetragonal phase at high fluorine content. Coupled X-ray/neutron Rietveld refinement establishes the end member as the anion-saturated oxyfluoride Ba 2 In 0.5 Sb 0.5 O 2 F 4 , and locates the three fully occupied anion sites of the tetragonal I 4 /mmm framework. The preferred O/F distribution, with oxide at the equatorial site and fluoride at the apical and interstitial sites, is supported by bond-valence-sums (BVSs) analysis of the refined interatomic distances and the corresponding global instability indices (GIIs), together with charge balance, since O and F cannot be reliably distinguished from their neutron scattering lengths alone. X-ray absorption near-edge structure (XANES) measurements support the retention of the formal In 3+ and Sb 5+ oxidation states upon fluorination.",
  "abstract_shown": true,
  "affiliations": [
    "Institute of Materials Science, Chemical Materials Synthesis, Heisenbergstrasse 3, Stuttgart, Germany, 70569",
    "Surface Science Laboratory, Technical University of Darmstadt, Peter-Grünberg-Straße 4, Darmstadt, Germany, 64287",
    "Institute for Inorganic Chemistry and Center for Sustainable Systems Design (CSSD, Paderborn University, Warburger Str. 100, Paderborn, Germany, 33098",
    "Department of Chemistry, Chair of Physical Chemistry III, University of Bayreuth, Universitätsstraße 30, Bayreuth, Germany, 95447",
    "Univ. Grenoble Alpes, CEA, CNRS, Grenoble INP, IRIG, 17 rue des Martyrs, Grenoble, France, F-38000",
    "Institut Laue–Langevin (ILL), 71 rue des Martyrs F-38000 Grenoble, France., Grenoble, France, F-38000",
    "Department of Chemistry, Inorganic Chemistry, Martin Luther University Halle-Wittenberg, Kurt-Mothes-Straße 2, Halle, Germany, 06120"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 15,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Shama Perween",
      "orcid": "0000-0001-9631-5995"
    },
    {
      "name": "Tolga Kocaer"
    },
    {
      "affs": [
        1
      ],
      "name": "Harol Moreno Fernández",
      "orcid": "0000-0002-4362-9488"
    },
    {
      "affs": [
        2
      ],
      "name": "Roland Schoch",
      "orcid": "0000-0003-2061-7289"
    },
    {
      "affs": [
        2
      ],
      "name": "Felix R. Fischer",
      "orcid": "0009-0008-0172-8067"
    },
    {
      "affs": [
        3
      ],
      "name": "Jana Timm",
      "orcid": "0000-0003-4728-2984"
    },
    {
      "affs": [
        0
      ],
      "name": "Rubén O. Miranda-Rosales",
      "orcid": "0009-0002-3432-9659"
    },
    {
      "affs": [
        0
      ],
      "name": "Xiangwei Guo",
      "orcid": "0009-0009-8517-2656"
    },
    {
      "affs": [
        4,
        5
      ],
      "name": "Ove Korjus",
      "orcid": "0000-0003-2151-0440"
    },
    {
      "affs": [
        5
      ],
      "name": "Clemens Ritter",
      "orcid": "0000-0003-3674-3378"
    },
    {
      "affs": [
        2
      ],
      "name": "Matthias Bauer",
      "orcid": "0000-0002-9294-6076"
    },
    {
      "affs": [
        0
      ],
      "name": "Oliver Clemens",
      "orcid": "0000-0002-0860-0911"
    },
    {
      "affs": [
        3
      ],
      "name": "Roland Marschall",
      "orcid": "0000-0002-1057-0459"
    },
    {
      "affs": [
        1
      ],
      "name": "Jan Philipp Hofmann",
      "orcid": "0000-0002-5765-1096"
    },
    {
      "affs": [
        6
      ],
      "name": "Jonas Jacobs",
      "orcid": "0000-0001-5473-9650"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/5fcy5mvew402w.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15007771/v2",
  "fulltext_url": null,
  "id": "5fcy5mvew402w",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15007771/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",
      "1604|Inorganic Fluorides and Related Compounds"
    ]
  ],
  "openalex": "W7213555170",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15007771/v2",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-18",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/5fcy5mvew402w.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:19Z",
      "native_id": "10.26434/chemrxiv.15007771",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15007771/v2"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1604|Inorganic Fluorides and Related Compounds",
      "subfield": "inorganic"
    }
  ],
  "title": "Topochemical Fluorination of the Ruddlesden−Popper In/Sb-Mixed Oxide Ba2In0.5Sb0.5O4; Staged Anion Insertion and Structural Evolution toward the Fluorine-Rich Oxyfluoride Ba2In0.5Sb0.5O2F4",
  "title_text": "Topochemical Fluorination of the Ruddlesden−Popper In/Sb-Mixed Oxide Ba2In0.5Sb0.5O4; Staged Anion Insertion and Structural Evolution toward the Fluorine-Rich Oxyfluoride Ba2In0.5Sb0.5O2F4",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:19Z",
  "url": "https://research.draconitic.com/paper/5fcy5mvew402w",
  "venue": "ChemRxiv",
  "versions": []
}