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Photoinduced Mo-CN bond breakage in octacyanomolybdate leading to spin triplet trapping

Abstract : The photoinduced properties of the octacoordinated complex K4MoIV(CN)8⋅2 H2O were studied by theoretical calculations, crystallography, and optical and magnetic measurements. The crystal structure recorded at 10 K after blue light irradiation reveals an heptacoordinated Mo(CN)7 species originating from the light‐induced cleavage of one Mo−CN bond, concomitant with the photoinduced formation of a paramagnetic signal. When this complex is heated to 70 K, it returns to its original diamagnetic ground state, demonstrating full reversibility. The photomagnetic properties show a partial conversion into a triplet state possessing significant magnetic anisotropy, which is in agreement with theoretical studies. Inspired by these results, we isolated the new compound [K(crypt‐222)]3[MoIV(CN)7]⋅3 CH3CN using a photochemical pathway, confirming that photodissociation leads to a stable heptacyanomolybdate(IV) species in solution.
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Xinghui Qi, Sébastien Pillet, Coen de Graaf, Michał Magott, El-Eulmi Bendeif, et al.. Photoinduced Mo-CN bond breakage in octacyanomolybdate leading to spin triplet trapping. Angewandte Chemie International Edition, Wiley-VCH Verlag, 2020, 59 (8), pp.3117-3121. ⟨10.1002/anie.201914527⟩. ⟨hal-02499555⟩

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