Institution: | 1. CNRS, Univ. Bordeaux, Bordeaux INP, ICMCB, UMR 5026, F-33600 Pessac, France;2. Université de Lorraine, CNRS, CRM2, Nancy, 54506 Vandoeuvre-les-Nancy, France;3. Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Carrer Marcellí Domingo 1, Tarragona, Spain;4. Jagiellonian University, Faculty of Chemistry, Gronostajowa 2, 30-387 Kraków, Poland;5. CNRS, Univ. Bordeaux, CRPP, UMR 5031, F-33600 Pessac, France;6. Sorbonne Université, IPCM-CNRS-UMR-8232, cc 229, 4 place Jussieu, 75252 Paris Cedex 05, France;7. CNRS, Univ. Bordeaux, Bordeaux INP, ICMCB, UMR 5026, F-33600 Pessac, France
Present address: Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033 Japan |
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. |