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Spin Crossover Behavior in a Homologous Series of Iron(II) Complexes Based on Functionalized Bipyridyl Ligands

Abstract : A series of bulky substituted bipyridine-related iron(II) complexes [Fe(HBpz)(L)] (pz = pyrazolyl) were prepared, where L = 5,5'-dimethyl-2,2'-bipyridine (bipy-CH, 1), L = dimethyl-2,2'-bipyridyl-5,5'-dicarboxylate (MeObpydc, 2), L = diethyl-2,2'-bipyridyl-5,5'-dicarboxylate (EtObpydc, 3), or L = diisopropyl-2,2'-bipyridine-5,5'-dicarboxylate ( i-PrObpydc, 4). The crystal structures of five new iron(II) complexes were determined by X-ray diffraction: those of 1, 3, and 4 and two modifications of 3 (3B) and 4 (4B). Complexes 1 and 3B display incomplete spin crossover (SCO) behavior because of a freezing-in effect, whereas 3 and 4B undergo gradual and incomplete SCO behaviors. Complexes 2 and 4 show a completely gradual and steep SCO, respectively. Such different SCO behaviors can be attributed to an electronic substituent effect in the bipyridyl ligand conformation and a crystal packing effect. Importantly, the electronic substituent effect of the isopropyl acetate group and C-H···O supramolecular interactions in 4 contribute to a highly cooperative behavior, which leads to an abrupt thermally induced spin transition.
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https://hal-univ-rennes1.archives-ouvertes.fr/hal-01879730
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Submitted on : Monday, September 24, 2018 - 11:32:54 AM
Last modification on : Monday, March 2, 2020 - 1:05:17 PM

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Shufang Xue, Yunnan Guo, Aurelian Rotaru, Helge Mueller-Bunz, Grace G. Morgan, et al.. Spin Crossover Behavior in a Homologous Series of Iron(II) Complexes Based on Functionalized Bipyridyl Ligands. Inorganic Chemistry, American Chemical Society, 2018, 57 (16), pp.9880-9891. ⟨10.1021/acs.inorgchem.8b00850⟩. ⟨hal-01879730⟩

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