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PreprintCC BYChemRxiv

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

  • Shama Perween1
  • Tolga Kocaer
  • Harol Moreno Fernández2
  • Roland Schoch3
  • Felix R. Fischer3
  • Jana Timm4
  • Rubén O. Miranda-Rosales1
  • Xiangwei Guo1
  • Ove Korjus5,6
  • Clemens Ritter6
  • Matthias Bauer3
  • Oliver Clemens1
3 more authors
  • Roland Marschall4
  • Jan Philipp Hofmann2
  • Jonas Jacobs7
7 affiliations
  1. 1Institute of Materials Science, Chemical Materials Synthesis, Heisenbergstrasse 3, Stuttgart, Germany, 70569
  2. 2Surface Science Laboratory, Technical University of Darmstadt, Peter-Grünberg-Straße 4, Darmstadt, Germany, 64287
  3. 3Institute for Inorganic Chemistry and Center for Sustainable Systems Design (CSSD, Paderborn University, Warburger Str. 100, Paderborn, Germany, 33098
  4. 4Department of Chemistry, Chair of Physical Chemistry III, University of Bayreuth, Universitätsstraße 30, Bayreuth, Germany, 95447
  5. 5Univ. Grenoble Alpes, CEA, CNRS, Grenoble INP, IRIG, 17 rue des Martyrs, Grenoble, France, F-38000
  6. 6Institut Laue–Langevin (ILL), 71 rue des Martyrs F-38000 Grenoble, France., Grenoble, France, F-38000
  7. 7Department of Chemistry, Inorganic Chemistry, Martin Luther University Halle-Wittenberg, Kurt-Mothes-Straße 2, Halle, Germany, 06120
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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.

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Cite

BibTeXRIS
BibTeX
@misc{perween2026topochemical,
  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}},
  author = {Shama Perween and Tolga Kocaer and Harol Moreno Fernández and Roland Schoch and Felix R. Fischer and Jana Timm and Rubén O. Miranda-Rosales and Xiangwei Guo and Ove Korjus and Clemens Ritter and Matthias Bauer and Oliver Clemens and Roland Marschall and Jan Philipp Hofmann and Jonas Jacobs},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15007771/v2},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15007771/v2},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - 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
AU  - Shama Perween
AU  - Tolga Kocaer
AU  - Harol Moreno Fernández
AU  - Roland Schoch
AU  - Felix R. Fischer
AU  - Jana Timm
AU  - Rubén O. Miranda-Rosales
AU  - Xiangwei Guo
AU  - Ove Korjus
AU  - Clemens Ritter
AU  - Matthias Bauer
AU  - Oliver Clemens
AU  - Roland Marschall
AU  - Jan Philipp Hofmann
AU  - Jonas Jacobs
PY  - 2026
DA  - 2026/09/18
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15007771/v2
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15007771/v2
AB  - 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.
ER  -