One-Dimensional Thiocyanato-Bridged Fe(II) Spin Crossover Cooperative Polymer With Unusual FeN5S Coordination Sphere

Abstract : We present here a novel example of spin crossover phenomenon on a Fe(II) one-dimensional chain with unusual N5S coordination sphere. The [{Fe(tpc-OMe)(NCS)(μ-NCS)}n] (1) compound was prepared using the tridentate tpc-OMe ligand (tpc-OMe = tris(2-pyridyl)methoxymethane), FeCl2·4H2O, and the KSCN salt. Crystallographic investigations revealed that the Fe(II) ions are connected by a single bridging NCS– ligand (μ-κN:κS-SCN coordination mode) to afford a zigzag neutral chain running along the [010] direction, in which the thiocyanato bridging groups adopt a cis head-to-tail configuration. The (N5S) metal environment arises from one thiocyanato-κS and two thiocyanato-κN ligands and from three pyridine of the fac-tpc-OMe tripodal ligand. This compound presents a unique extension of Fe(II) binuclear complexes into linear chains built on similar tripodal ligands and bridging thiocyanate anions. Compound 1 shows a spin crossover (SCO) behavior which has been evidenced by magnetic, calorimetric, and structural investigations, revealing a sharp cooperative spin transition with a transition temperature of ca. 199 K. Temperature scan rate studies revealed a very narrow hysteresis loop (∼1 K wide). Photoswitching of this compound was also performed, evidencing a very fast relaxation process at low temperature. Among other factors, the linearity of the N-bound terminal thiocyanato ligand appears as the main structural characteristic at the origin of the presence of the SCO transition in compound 1 and in the two others Fe(II) previous systems involving thiocyanato-bridges and tripodal tris(2-pyridyl)methane ligands.
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One-Dimensional Thiocyanato-Br...
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Kahina Nebbali, Cle Donacier Mekuimemba, Catherine Charles, Said Yefsah, Guillaume Chastanet, et al.. One-Dimensional Thiocyanato-Bridged Fe(II) Spin Crossover Cooperative Polymer With Unusual FeN5S Coordination Sphere. Inorganic Chemistry, American Chemical Society, 2018, 57 (19), pp.12338-12346. 〈10.1021/acs.inorgchem.8b02061〉. 〈hal-01872926〉



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