Large Orbital Magnetic Moment Measured in the [TpFeIII(CN)3]− Precursor of Photomagnetic Molecular Prussian Blue Analogues

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• 作者：Sadaf Fatima Jafri ; Evangelia S. Koumousi ; Philippe Sainctavit ; Amélie Juhin ; Vivien Schuler ; Oana Bunǎu ; Dmitri Mitcov ; Pierre Dechambenoit ; Corine Mathonière ; Rodolphe Clérac ; Edwige Otero ; Philippe Ohresser ; Christophe Cartier dit Moulin ; Marie-Anne Arrio
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：July 18, 2016
• 年：2016
• 卷：55
• 期：14
• 页码：6980-6987
• 全文大小：379K
• 年卷期：0
• ISSN：1520-510X

文摘

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 L_2,3 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 μ_B 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.