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<p>Metal-organic compounds that feature magnetic bistability have been proposed as bits for magnetic storage, but progress has been slow. Four-coordinate cobalt(II) complexes feature high inversion barriers of the magnetic moment, but they lack magnetic bistability. Developing radical-bridged polynuclear systems is a promising strategy to encounter this; however detailed investigations of such species are scarce. We report an air-stable radical-bridged dinuclear cobalt(II) complex, studied by a combination of magnetometry and spectroscopy. Fits of the data give <i>D</i>&#xa0;=&#xa0;−113 cm<sup>−1</sup> for the zero-field splitting (ZFS) and <i>J</i>&#xa0;=&#xa0;390 cm<sup>−1</sup> for the metal–radical exchange. Ab initio investigations reveal first-order spin–orbit coupling of the quasi-degenerate <InlineEquation ID="IEq1"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="41467_2025_57210_Article_IEq1.gif" Format="GIF" Height="20" Rendition="HTML" Resolution="72" Type="Linedraw" Width="43" /> </InlineMediaObject> <EquationSource Format="TEX">\({{{{\rm{d}}}}}_{{x}^{2}-{y}^{2}}\)</EquationSource> <EquationSource Format="MATHML"><math> <msub> <mrow> <mi mathvariant="normal">d</mi> </mrow> <mrow> <msup> <mrow> <mi>x</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msup> <mo>−</mo> <msup> <mrow> <mi>y</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msup> </mrow> </msub> </math></EquationSource> </InlineEquation> and d<sub><i>x</i><i>y</i></sub> orbitals to be at the heart of the large ZFS. The corresponding transitions are spectroscopically observed, as are transitions related to the exchange coupling. Finally, signatures of spin-phonon coupling are observed and theoretically analyzed. Furthermore, we demonstrate that the spectral features are not predominantly spin excitations, but largely vibrational in character.</p>

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Electronic structure of mononuclear and radical-bridged dinuclear cobalt(II) single-molecule magnets

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年3月4日

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  • David Hunger,
  • Julia Netz,
  • Simon Suhr,
  • Komalavalli Thirunavukkuarasu,
  • Hans Engelkamp,
  • Björn Fåk,
  • Uta Albold,
  • Julia Beerhues,
  • Wolfgang Frey,
  • Ingo Hartenbach,
  • Michael Schulze,
  • Wolfgang Wernsdorfer,
  • Biprajit Sarkar,
  • Andreas Köhn,
  • Joris van Slageren

摘要

Metal-organic compounds that feature magnetic bistability have been proposed as bits for magnetic storage, but progress has been slow. Four-coordinate cobalt(II) complexes feature high inversion barriers of the magnetic moment, but they lack magnetic bistability. Developing radical-bridged polynuclear systems is a promising strategy to encounter this; however detailed investigations of such species are scarce. We report an air-stable radical-bridged dinuclear cobalt(II) complex, studied by a combination of magnetometry and spectroscopy. Fits of the data give D = −113 cm−1 for the zero-field splitting (ZFS) and J = 390 cm−1 for the metal–radical exchange. Ab initio investigations reveal first-order spin–orbit coupling of the quasi-degenerate \({{{{\rm{d}}}}}_{{x}^{2}-{y}^{2}}\) d x 2 − y 2 and dxy orbitals to be at the heart of the large ZFS. The corresponding transitions are spectroscopically observed, as are transitions related to the exchange coupling. Finally, signatures of spin-phonon coupling are observed and theoretically analyzed. Furthermore, we demonstrate that the spectral features are not predominantly spin excitations, but largely vibrational in character.