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

Michał Magott, Mirosław Arczyński, Leszek Malec, Michał Rams, Mathieu Rouzières, Andrei Rogalev, Fabrice Wilhelm, Itziar Oyarzabal, Thomas Lohmiller, Alexander Schnegg, Coen Graaf, Corine Mathonière, Rodolphe Clérac and Dawid Pinkowicz ()
Additional contact information
Michał Magott: Gronostajowa 2
Mirosław Arczyński: Gronostajowa 2
Leszek Malec: Gronostajowa 2
Michał Rams: Łojasiewicza 11
Mathieu Rouzières: UMR 5031
Andrei Rogalev: 71 av. des Martyrs
Fabrice Wilhelm: 71 av. des Martyrs
Itziar Oyarzabal: UPV/EHU Science Park
Thomas Lohmiller: Helmholtz Zentrum Berlin für Materialien und Energie GmbH
Alexander Schnegg: EPR Research Group
Coen Graaf: C. Marcellí Domingo 1
Corine Mathonière: UMR 5031
Rodolphe Clérac: UMR 5031
Dawid Pinkowicz: Gronostajowa 2

Nature Communications, 2025, vol. 16, issue 1, 1-10

Abstract: Abstract 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.

Date: 2025
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DOI: 10.1038/s41467-025-63523-x

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