Photoinduced Mo−CN Bond Breakage in Octacyanomolybdate Leading to Spin Triplet Trapping |
| |
| Authors: | Xinghui Qi Sbastien Pillet Coen de Graaf Micha&#x; Magott El‐Eulmi Bendeif Philippe Guionneau Mathieu Rouzires Valrie Marvaud Olaf Stefa&#x;czyk Dawid Pinkowicz Corine Mathonire |
| |
| Institution: | Xinghui Qi,Sébastien Pillet,Coen de Graaf,Micha? Magott,El‐Eulmi Bendeif,Philippe Guionneau,Mathieu Rouzières,Valérie Marvaud,Olaf Stefańczyk,Dawid Pinkowicz,Corine Mathonière |
| |
| 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)]3MoIV(CN)7]?3 CH3CN using a photochemical pathway, confirming that photodissociation leads to a stable heptacyanomolybdate(IV) species in solution. |
| |
| Keywords: | cyanides magnetic properties molybdenum photochemistry X-ray diffraction |
|
|
