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Photoinduced magnetization has been recently evidenced by Hashimoto et al. in CoFe Prussian blue analogues. We synthesized three compounds with a variable cobalt environment to point out the conditions required to observe the photoinduced magnetization. Structure and electronic structure of the compounds have been investigated combining XANES, infrared spectroscopy, and powder X-ray diffraction experiments. Magnetization as a function of temperature before and after irradiation showed that diamagnetic pairs Co III -NC-Fe II are necessary for the existence of the photoinduced magnetization, but their presence is not a sufficient condition. The role of hexacyanoferrate vacancies in the phenomenon is pointed out.

Molecular-based magnets with high magnetic-ordering temperatures, T(c), can be obtained by mild chemistry methods by focusing on the bimetallic and mixed-valence transition metal micro-cyanide of the Prussian blue family. A simple orbital model was used to predict the electronic structure of the metal ions required to achieve a high ordering temperature. The synthesis and magnetic properties of two compounds, [Cr(5)(CN)(12)].10H(2)O and Cs(0.75) [Cr(2.125)(CN)(6)].5H(2)O, which exhibited magnetic-ordering temperatures of 240 and 190 kelvin, respectively, are reported, together with the strategy for further work.

As materials science is moving towards the synthesis, the study and the processing of new materials exhibiting well-defined and complex functions, the synthesis of new multifunctional materials is one of the important challenges. One of these complex physical properties is magneto-chiral dichroism which arises, at second order, from the coexistence of spatial asymmetry and magnetization in a material. Herein we report the first measurement of strong magneto-chiral dichroism in an enantiopure chiral ferromagnet. The ab initio synthesis of the enantiopure chiral ferromagnet is based on an enantioselective self-assembly, where a resolved chiral quaternary ammonium cation imposes the absolute configurations of the metal centres within chromium-manganese two-dimensional oxalate layers. The ferromagnetic interaction between Cr(III) and Mn(II) ions leads to a Curie temperature of 7 K. The magneto-chiral dichroic effect is enhanced by a factor of 17 when entering into the ferromagnetic phase.

We synthesized a series of CoFe Prussian blue analogues along which we tuned the amount of cesium cations inserted in the tetrahedral sites of the structure. Structure and electronic structure have been investigated, combining XANES, infrared spectroscopy, powder X-ray diffraction experiments, and magnetization measurements. The change of the magnetization induced by light along the series shows that the efficiency of the photoinduced magnetization, evidenced a few years ago in similar compounds by Hashimoto et al. (Sato, O.; Iyoda, T.; Fujishima, A.; Hashimoto, K. Science 1996, 272, 704-705; Sato, O.; Einaga, Y.; Iyoda, T.; Fujishima, A.; Hashimoto, K. J. Electrochem. Soc. 1997, 144, L11-L13; Sato, O.; Einaga, Y.; Iyoda, T.; Fujishima, A.; Hashimoto, K. J. Phys. Chem. B 1997, 101, 3903-3905; Einaga, Y.; Ohkoshi, S.-I.; Sato, O.; Fujishima, A.; Hashimoto, K. Chem. Lett. 1998, 585-586; and Sato, O.; Einaga, Y.; Fujishima, A.; Hashimoto, K. Inorg. Chem. 1999, 38, 4405-4412), depends on a compromise between the number of excitable diamagnetic pairs and the amount of [Fe(CN)6] vacancies giving the network flexibility. Besides the efficiency of the photoinduced process, the amount of [Fe(CN)6] vacancies also controls a thermally induced electron transfer.

A CoFe Prussian blue analogue Rb 1.8 Co 4 [Fe(CN) 6 ] 3.3 ‚13H 2 O was synthesized, which presents an important photomagnetic effect. The electronic structure and the local structure of the ground and of the excited states have been investigated. X-ray absorption spectroscopy measurements at the Co and Fe L 2,3 edges and cobalt K-edge (XANES and EXAFS) evidence the local electronic transfer and the spin change of the cobalt ions induced by irradiation. We observed a 0.19 Å increase of the Co-N bond length, associated with the transformation of Co III low spin to Co II high spin. The Co II /Co III ratio has been evaluated as a function of the irradiation time and revealed as an important parameter to understanding the bulk magnetic properties. The combined role of the diamagnetic Fe II -Co III pairs and hexacyanoferrate(III) vacancies is locally evidenced. This work is a new step in the understanding of the photoinduced electron transfer.

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