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PreprintCC BYChemRxiv

Linking electronic and geometrical structure to local magnetism in lanthanide hexacyanoferrates by paramagnetic solid-state NMR

  • Wassilios Papawassiliou1
  • Gabriel Balavoine1
  • Euan N. Bassey1
  • Ntaniela Kalemai2,3
  • Nikolia Lalioti2,3
  • Andrew J. Pell1,4
4 affiliations
  1. 1Centre de RMN à Très Hauts Champs de Lyon (UMR 5280 CNRS / ENS Lyon / Lyon 1 Université, 5 rue de la Doua, Villeurbanne, France, 69100
  2. 2Department of Chemistry, Laboratory of Inorganic Chemistry
  3. 3University of Patras
  4. 4Institut Universitaire de France (IUF
Open at sourceDOICite

Abstract

Lanthanide hexacyanoferrates, LnFe(CN)6·xH2O, combine the structural versatility of cyanidebridged frameworks with the strong spin–orbit coupling and crystal-field effects of lanthanide ions. Yet, the local (ion-specific) origins of the magnetic response of these materials remain difficult to resolve by conventional solid-state chemistry techniques. Here, we report the 1H and 13C solid-state nuclear magnetic resonance (NMR) spectra of LnFe(CN)6·xH2O (Ln = La to Yb), with assignments supported by first-principles calculations and optical spectroscopy. We interpret the 1H NMR spectra in terms of free (interstitial) and bound (Ln-coordinated) water environments within the porous framework. The 1H shifts and shift anisotropies scale approximately linearly with the lanthanide Bleaney coefficients, establishing a direct and quantifiable link between 1H spectra and single-ion anisotropy. Using 13C NMR spectra, we are able to isolate the impact of Ln composition, despite the Ln contribution comprising only a small fraction (up to 3%) of the total paramagnetic NMR shift. The 13C shift anisotropy also tracks linearly with the Bleaney coefficients, whilst the trend against the isotropic shift is weaker, underlining the site-specific effect of Fermi contact and dipolar contributions to the total shift. Together, out results establish solid-state NMR spectroscopy as a sensitive and quantitative probe of single-ion anisotropy in cyanide-based frameworks.

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Cite

BibTeXRIS
BibTeX
@misc{papawassiliou2026linking,
  title = {{Linking electronic and geometrical structure to local magnetism in lanthanide hexacyanoferrates by paramagnetic solid-state NMR}},
  author = {Wassilios Papawassiliou and Gabriel Balavoine and Euan N. Bassey and Ntaniela Kalemai and Nikolia Lalioti and Andrew J. Pell},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15008879/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008879/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Linking electronic and geometrical structure to local magnetism in lanthanide hexacyanoferrates by paramagnetic solid-state NMR
AU  - Wassilios Papawassiliou
AU  - Gabriel Balavoine
AU  - Euan N. Bassey
AU  - Ntaniela Kalemai
AU  - Nikolia Lalioti
AU  - Andrew J. Pell
PY  - 2026
DA  - 2026/09/15
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15008879/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008879/v1
AB  - Lanthanide hexacyanoferrates, LnFe(CN)6·xH2O, combine the structural versatility of cyanidebridged frameworks with the strong spin–orbit coupling and crystal-field effects of lanthanide ions. Yet, the local (ion-specific) origins of the magnetic response of these materials remain difficult to resolve by conventional solid-state chemistry techniques. Here, we report the 1H and 13C solid-state nuclear magnetic resonance (NMR) spectra of LnFe(CN)6·xH2O (Ln = La to Yb), with assignments supported by first-principles calculations and optical spectroscopy. We interpret the 1H NMR spectra in terms of free (interstitial) and bound (Ln-coordinated) water environments within the porous framework. The 1H shifts and shift anisotropies scale approximately linearly with the lanthanide Bleaney coefficients, establishing a direct and quantifiable link between 1H spectra and single-ion anisotropy. Using 13C NMR spectra, we are able to isolate the impact of Ln composition, despite the Ln contribution comprising only a small fraction (up to 3%) of the total paramagnetic NMR shift. The 13C shift anisotropy also tracks linearly with the Bleaney coefficients, whilst the trend against the isotropic shift is weaker, underlining the site-specific effect of Fermi contact and dipolar contributions to the total shift. Together, out results establish solid-state NMR spectroscopy as a sensitive and quantitative probe of single-ion anisotropy in cyanide-based frameworks.
ER  -