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On the magnetic coupling and spin crossover behavior in complexes containing the head-to-tail [FeII2(-SCN)2] bridging unit: A magneto-structural experimental and theoretical study

Abstract : A new dinuclear complex [{Fe(tpc-OBn)(NCS)(μ-NCS)}2] (1) based on the tripodal tpc-OBn ligand (tpc-OBn = tris(2-pyridyl)benzyloxymethane), containing bridging μ-κN:κS-SCN and terminal κN-SCN thiocyanate ligands, has been prepared and characterized by single crystal X-ray diffraction, magnetic studies, and DFT theoretical calculations. This complex represents the first example of dinuclear FeII complex with double μ-κN:κS-SCN bridges in a head-to-tail configuration that exhibits ferromagnetic coupling between metal ions (JFeFe = +1.08 cm–1). Experimental and theoretical magnetostructural studies on this kind of infrequent FeII dinuclear complex containing a centrosymmetrically [Fe2(μ-SCN)2] bridging fragment show that the magnitude and sign of the magnetic coupling parameter, JFeFe, depend to a large extent on the Fe–N–C (α) angle, so that JFeFe decreases linearly when α decreases. The calculated crossover point below which the magnetic interactions change from ferromagnetic to antiferromagnetic is found at 162.3°. In addition, experimental results obtained in this work and those reported in the literature suggest that large Ntripodal–FeII distances and bent N-bound terminal κN-SCN ligands favor the high spin state of the FeII ions, while short Ntripodal–FeII distances and almost linear Fe–N–C angles favor a stronger ligand field, which enables the FeII ions to show spin crossover (SCO) behavior.
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Submitted on : Wednesday, February 7, 2018 - 10:03:45 AM
Last modification on : Thursday, November 29, 2018 - 4:09:15 PM

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Cle Donacier Mekuimemba, Françoise Conan, Antonio J. Mota, Maria A. Palacios, Enrique Colacio, et al.. On the magnetic coupling and spin crossover behavior in complexes containing the head-to-tail [FeII2(-SCN)2] bridging unit: A magneto-structural experimental and theoretical study . Inorganic Chemistry, American Chemical Society, In press, ⟨10.1021/acs.inorgchem.7b03082⟩. ⟨hal-01702694⟩

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