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Supramolecular Iron Metallocubanes Exhibiting Site-Selective Thermal and Light-Induced Spin-Crossover

  • Izar Capel Berdiell
    Izar Capel Berdiell
    School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, U.K.
  • Tim Hochdörffer
    Tim Hochdörffer
    Department of Physics, Technical University of Kaiserslautern, Erwin Schrödinger Straße 46, D-67663 Kaiserslautern, Germany
  • Cédric Desplanches
    Cédric Desplanches
    CNRS, Université de Bordeaux, ICMCB, UMR 5026, F-33600 Pessac, France
  • Rafal Kulmaczewski
    Rafal Kulmaczewski
    School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, U.K.
  • Namrah Shahid
    Namrah Shahid
    School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, U.K.
  • Juliusz A. Wolny
    Juliusz A. Wolny
    Department of Physics, Technical University of Kaiserslautern, Erwin Schrödinger Straße 46, D-67663 Kaiserslautern, Germany
  • Stuart L. Warriner
    Stuart L. Warriner
    School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, U.K.
  • Oscar Cespedes
    Oscar Cespedes
    School of Physics and Astronomy, EC Stoner Building, University of Leeds, Leeds LS2 9JT, U.K.
  • Volker Schünemann
    Volker Schünemann
    Department of Physics, Technical University of Kaiserslautern, Erwin Schrödinger Straße 46, D-67663 Kaiserslautern, Germany
  • Guillaume Chastanet*
    Guillaume Chastanet
    CNRS, Université de Bordeaux, ICMCB, UMR 5026, F-33600 Pessac, France
    *[email protected]
  • , and 
  • Malcolm A. Halcrow*
    Malcolm A. Halcrow
    School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, U.K.
    *[email protected]
Cite this: J. Am. Chem. Soc. 2019, 141, 47, 18759–18770
Publication Date (Web):November 5, 2019
https://doi.org/10.1021/jacs.9b08862
Copyright © 2019 American Chemical Society

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    Supporting Info (13)»

    Abstract

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    Treatment of Fe[BF4]2·6H2O with 4,6-di(pyrazol-1-yl)-1H-pyrimid-2-one (HL1) or 4,6-di(4-methylpyrazol-1-yl)-1H-pyrimid-2-one (HL2) affords solvated crystals of [{FeIII(OH2)6}⊂FeII8(μ-L)12][BF4]7 (1, HL = HL1; 2, HL = HL2). The centrosymmetric complexes contain a cubic arrangement of iron(II) centers, with bis-bidentate [L] ligands bridging the edges of the cube. The encapsulated [Fe(OH2)6]3+ moiety templates the assembly through 12 O–H···O hydrogen bonds to the [L] hydroxylate groups. All four unique iron(II) ions in the cages are crystallographically high-spin at 250 K, but they undergo a gradual high → low spin-crossover on cooling, which is predominantly centered on one iron(II) site and its symmetry-related congener. This was confirmed by magnetic susceptibility data, light-induced excited spin state trapping (LIESST) effect measurements, and, for 1, Mössbauer spectroscopy and diffuse reflectance data. The clusters are stable in MeCN solution, and 1 remains high-spin above 240 K in that solvent. The cubane assembly was not obtained from reactions using other iron(II) salts or 4,6-di(pyrazol-1-yl)pyrimidine ligands, highlighting the importance of hydrogen bonding in templating the cubane assembly.

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.9b08862. CCDC 1861171–1861177 and 1938349–1938353 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Center, 12 Union Road, Cambridge CB2 1EZ, UK; fax: + 44 1223 336033.

    • Full experimental procedures and analytical characterization for the new compounds; crystallographic figures and tables for the ligand and complex structures; Mössbauer spectra and simulated parameters; and additional solid and solution phase characterization data, including Figures S1–S31 and Tables S1–S21 (PDF)

    • X-ray crystallographic data for HL1 (CIF)

    • X-ray crystallographic data for HL2 (CIF)

    • X-ray crystallographic data for 1 at 100 K (CIF)

    • X-ray crystallographic data for 1 at 150 K (CIF)

    • X-ray crystallographic data for 1 at 200 K (CIF)

    • X-ray crystallographic data for 1 at 250 K (CIF)

    • X-ray crystallographic data for 2 at 125 K (CIF)

    • X-ray crystallographic data for 2 at 200 K (CIF)

    • X-ray crystallographic data for 2 at 250 K (CIF)

    • X-ray crystallographic data for 3 (CIF)

    • X-ray crystallographic data for 4 (CIF)

    • X-ray crystallographic data for 5 (CIF)

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