title: Large Orbital Magnetic Moment Measured in the [TpFe(III)(CN)3](-) Precursor of Photomagnetic Molecular Prussian Blue Analogues.
abstract: Photomagnetism in three-dimensional Co/Fe Prussian blue analogues is a complex phenomenon, whose detailed mechanism is not yet fully understood. Recently, researchers have been able to prepare molecular fragments of these networks using a building block synthetic approach from mononuclear precursors. The main objective in this strategy is to isolate the smallest units that show an intramolecular electron transfer to have a better understanding of the electronic processes. A prior requirement to the development of this kind of system is to understand to what extent electronic and magnetic properties are inherited from the corresponding precursors. In this work, we investigate the electronic and magnetic properties of the FeTp precursor (N(C4H9)4)[TpFe(III)(CN)3], (Tp being tris-pyrazolyl borate) of a recently reported binuclear cyanido-bridged Fe/Co complex. X-ray absorption spectroscopy and X-ray magnetic circular dichroism measurements at the Fe L2,3 edges (2p → 3d) supported by ligand field multiplet calculations have allowed to determine the spin and orbit magnetic moments. Inaccuracy of the spin sum rule in the case of low-spin Fe(III) ion was demonstrated. An exceptionally large value of the orbital magnetic moment is found (0.9 μB at T = 2 K and B = 6.5 T) that is likely to play an important role in the magnetic and photomagnetic properties of molecular Fe/Co Prussian blue analogues.
authors.affiliation: Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie, UMR7590, CNRS, UPMC, IRD, MNHN , 75252 Paris Cedex 05, France.
authors.forename: Sadaf Fatima
authors.initials: SF
authors.lastname: Jafri
authors.affiliation: CNRS, ICMCB, UPR 9048 , F-33600 Pessac, France.|Univ. Bordeaux, ICMCB, UPR 9048 , F-33600 Pessac, France.|CNRS, CRPP, UPR 8641 , F-33600 Pessac, France.|Univ. Bordeaux, CRPP, UPR 8641 , F-33600 Pessac, France.
authors.forename: Evangelia S
authors.initials: ES
authors.lastname: Koumousi
authors.affiliation: Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie, UMR7590, CNRS, UPMC, IRD, MNHN , 75252 Paris Cedex 05, France.|Synchrotron SOLEIL , L'Orme des Merisiers, 91190 Saint-Aubin, France.
authors.forename: Philippe
authors.initials: P
authors.lastname: Sainctavit
authors.affiliation: Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie, UMR7590, CNRS, UPMC, IRD, MNHN , 75252 Paris Cedex 05, France.
authors.forename: Amélie
authors.initials: A
authors.lastname: Juhin
authors.affiliation: Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie, UMR7590, CNRS, UPMC, IRD, MNHN , 75252 Paris Cedex 05, France.
authors.forename: Vivien
authors.initials: V
authors.lastname: Schuler
authors.affiliation: Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie, UMR7590, CNRS, UPMC, IRD, MNHN , 75252 Paris Cedex 05, France.
authors.forename: Oana
authors.initials: O
authors.lastname: Bun U
authors.affiliation: CNRS, CRPP, UPR 8641 , F-33600 Pessac, France.|Univ. Bordeaux, CRPP, UPR 8641 , F-33600 Pessac, France.
authors.forename: Dmitri
authors.initials: D
authors.lastname: Mitcov
authors.affiliation: CNRS, CRPP, UPR 8641 , F-33600 Pessac, France.|Univ. Bordeaux, CRPP, UPR 8641 , F-33600 Pessac, France.
authors.forename: Pierre
authors.initials: P
authors.lastname: Dechambenoit
authors.affiliation: CNRS, ICMCB, UPR 9048 , F-33600 Pessac, France.|Univ. Bordeaux, ICMCB, UPR 9048 , F-33600 Pessac, France.
authors.forename: Corine
authors.initials: C
authors.lastname: Mathonière
authors.affiliation: CNRS, CRPP, UPR 8641 , F-33600 Pessac, France.|Univ. Bordeaux, CRPP, UPR 8641 , F-33600 Pessac, France.
authors.forename: Rodolphe
authors.initials: R
authors.lastname: Clérac
authors.affiliation: Synchrotron SOLEIL , L'Orme des Merisiers, 91190 Saint-Aubin, France.
authors.forename: Edwige
authors.initials: E
authors.lastname: Otero
authors.affiliation: Synchrotron SOLEIL , L'Orme des Merisiers, 91190 Saint-Aubin, France.
authors.forename: Philippe
authors.initials: P
authors.lastname: Ohresser
authors.affiliation: CNRS, UMR 8232, Institut Parisien de Chimie Moléculaire , F-75005 Paris, France.|Sorbonne Universités, UPMC Univ. Paris 06, UMR 8232, IPCM , F-75005 Paris, France.
authors.forename: Christophe
authors.initials: C
authors.lastname: Cartier Dit Moulin
authors.affiliation: Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie, UMR7590, CNRS, UPMC, IRD, MNHN , 75252 Paris Cedex 05, France.
authors.forename: Marie-Anne
authors.initials: MA
authors.lastname: Arrio