QI, Xinghui; PILLET, Sébastien; DE GRAAF, Coen; MAGOTT, Michał; BENDEIF, El-Eulmi; GUIONNEAU, Philippe; ROUZIÈRES, Mathieu; MARVAUD, Valerie; STEFAŃCZYK, Olaf; PINKOWICZ, Dawid; MATHONIÈRE, Corine

doi:10.1002/anie.201914527

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QI, Xinghui
Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB]

PILLET, Sébastien
Cristallographie, Résonance Magnétique et Modélisations [CRM2]

DE GRAAF, Coen
Institució Catalana de Recerca i Estudis Avançats = Catalan Institution for Research and Advanced Studies [ICREA]

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Angewandte Chemie International Edition. 2020-02-17, vol. 59, n° 8, p. 3117-3121

Wiley-VCH Verlag

Résumé en anglais

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.< Réduire

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http://dx.doi.org/10.1002/anie.201914527

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Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB) - UMR 5026