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Photoinduced Mo−CN Bond Breakage in Octacyanomolybdate Leading to Spin Triplet Trapping
Author(s) -
Qi Xinghui,
Pillet Sébastien,
Graaf Coen,
Magott Michał,
Bendeif ElEulmi,
Guionneau Philippe,
Rouzières Mathieu,
Marvaud Valérie,
Stefańczyk Olaf,
Pinkowicz Dawid,
Mathonière Corine
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201914527
Subject(s) - chemistry , photochemistry , diamagnetism , electron paramagnetic resonance , paramagnetism , photodissociation , photoinduced electron transfer , anisotropy , crystallography , bond cleavage , ground state , triplet state , nuclear magnetic resonance , molecule , electron transfer , atomic physics , condensed matter physics , biochemistry , physics , organic chemistry , quantum mechanics , magnetic field , catalysis
The photoinduced properties of the octacoordinated complex K 4 Mo IV (CN) 8 ⋅2 H 2 O 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 [Mo IV (CN) 7 ]⋅3 CH 3 CN using a photochemical pathway, confirming that photodissociation leads to a stable heptacyanomolybdate(IV) species in solution.