{
  "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.",
  "abstract_shown": true,
  "affiliations": [
    "Centre de RMN à Très Hauts Champs de Lyon (UMR 5280 CNRS / ENS Lyon / Lyon 1 Université, 5 rue de la Doua, Villeurbanne, France, 69100",
    "Department of Chemistry, Laboratory of Inorganic Chemistry",
    "University of Patras",
    "Institut Universitaire de France (IUF"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 6,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Wassilios Papawassiliou"
    },
    {
      "affs": [
        0
      ],
      "name": "Gabriel Balavoine"
    },
    {
      "affs": [
        0
      ],
      "name": "Euan N. Bassey"
    },
    {
      "affs": [
        1,
        2
      ],
      "name": "Ntaniela Kalemai"
    },
    {
      "affs": [
        1,
        2
      ],
      "name": "Nikolia Lalioti"
    },
    {
      "affs": [
        0,
        3
      ],
      "name": "Andrew J. Pell",
      "orcid": "0000-0002-2542-8113"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/9w6eq22we0tkx.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15008879/v1",
  "fulltext_url": null,
  "id": "9w6eq22we0tkx",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008879/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",
      "2504|Magnetism in coordination complexes"
    ]
  ],
  "openalex": "W7213282635",
  "pdf_url": null,
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-15",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/9w6eq22we0tkx.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:19Z",
      "native_id": "10.26434/chemrxiv.15008879",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008879/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:2504|Magnetism in coordination complexes",
      "subfield": "materials-polymers"
    }
  ],
  "title": "Linking electronic and geometrical structure to local magnetism in lanthanide hexacyanoferrates by paramagnetic solid-state NMR",
  "title_text": "Linking electronic and geometrical structure to local magnetism in lanthanide hexacyanoferrates by paramagnetic solid-state NMR",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:19Z",
  "url": "https://research.draconitic.com/paper/9w6eq22we0tkx",
  "venue": "ChemRxiv",
  "versions": []
}