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<p>Manipulating the physical properties of solid matter using only photons is a major challenge in materials science. However, achieving such control over a chemical reaction in the solid state is even more challenging. Here we demonstrate the reversible photochemistry occurring in a single crystal of a simple cyanide complex, K<sub>4</sub>[Mo<sup>III</sup>(CN)<sub>7</sub>]·2H<sub>2</sub>O. Upon exposure to visible light at different wavelengths, a reversible breaking and reformation of dative bonds is triggered, resulting in a photoswitching of the Mo<sup>III</sup> coordination geometry between 6- and 7-coordinate. This transformation, in turn, induces a spin state change. The observed solid-state photochemical reactivity is robust, quantitative and occurs at a record-high temperature. It paves the way for the development of new photo-switchable high-temperature magnets and nanomagnets.</p>

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Reversible single crystal photochemistry and spin state switching in a metal-cyanide complex

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年9月29日

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  • Michał Magott,
  • Mirosław Arczyński,
  • Leszek Malec,
  • Michał Rams,
  • Mathieu Rouzières,
  • Andrei Rogalev,
  • Fabrice Wilhelm,
  • Itziar Oyarzabal,
  • Thomas Lohmiller,
  • Alexander Schnegg,
  • Coen de Graaf,
  • Corine Mathonière,
  • Rodolphe Clérac,
  • Dawid Pinkowicz

摘要

Manipulating the physical properties of solid matter using only photons is a major challenge in materials science. However, achieving such control over a chemical reaction in the solid state is even more challenging. Here we demonstrate the reversible photochemistry occurring in a single crystal of a simple cyanide complex, K4[MoIII(CN)7]·2H2O. Upon exposure to visible light at different wavelengths, a reversible breaking and reformation of dative bonds is triggered, resulting in a photoswitching of the MoIII coordination geometry between 6- and 7-coordinate. This transformation, in turn, induces a spin state change. The observed solid-state photochemical reactivity is robust, quantitative and occurs at a record-high temperature. It paves the way for the development of new photo-switchable high-temperature magnets and nanomagnets.