In Situ Ligand Transformation for Two-Step Spin Crossover in Fe[M(CN)] (M = Mo, Nb) Cyanido-Bridged Frameworks.

Authors:
Szymon Chorazy
Szymon Chorazy
Jagiellonian Univ.
Poland
Kenta Imoto
Kenta Imoto
School of Science
Japan
Takashi Fujimoto
Takashi Fujimoto
Tokyo Women's Medical University Medical Center East
Japan
Koji Nakabayashi
Koji Nakabayashi
Kobe University Graduate School of Medicine
Japan
Jan Stanek
Jan Stanek
University of Oxford
Poland
Barbara Sieklucka
Barbara Sieklucka
Jagiellonian University
Kraków | Poland

Inorg Chem 2019 May 19;58(9):6052-6063. Epub 2019 Apr 19.

Department of Chemistry, School of Science , The University of Tokyo , 7-3-1 Hongo , Bunkyo-ku, Tokyo 113-0033 , Japan.

We report a unique synthetic route toward the multistep spin crossover (SCO) effect induced by utilizing the partial ligand transformation during the crystallization process, which leads to the incorporation of three different Fe complexes into a single coordination framework. The 3-acetoxypyridine (3-OAcpy) molecules were introduced to the self-assembled Fe-[M(CN)] (M = Mo, Nb) system in the aqueous solution which results in the partial hydrolysis of the ligand into 3-hydroxypyridine (3-OHpy). It gives two novel isostructural three-dimensional {Fe(3-OAcpy)(3-OHpy)[M(CN)]}· nHO (M = Mo, n = 0, FeMo; M = Nb, n = 1, FeNb) coordination frameworks. They exhibit an unprecedented cyanido-bridged skeleton composed of {FeM} coordination nanotubes bonded by additional Fe complexes. These frameworks contain three types of Fe sites differing in the attached organic ligands, [Fe1(3-OAcpy)(μ-NC)], [Fe2(3-OHpy)(μ-NC)], and [Fe3(3-OAcpy)(3-OHpy)(μ-NC)], which lead to the thermal two-step Fe SCO, as proven by X-ray diffraction, magnetic susceptibility, UV-vis-NIR optical absorption, and Fe Mössbauer spectroscopy studies. The first step of SCO, going from room temperature to the 150-170 K range with transition temperatures of 245(5) and 283(5) K for FeMo and FeNb, respectively, is related to Fe1 sites, while the second step, occurring at the 50-140 K range with transition temperatures of 70(5) and 80(5) K for FeMo and FeNb, respectively, is related to Fe2 sites. The Fe3 site with both 3-OAcpy and 3-OHpy ligands does not undergo the SCO at all. The observed two-step SCO phenomenon is explained by the differences in the ligand field strength of the Fe complexes and the role of their alignment in the coordination framework. The simultaneous application of two related pyridine derivatives is the efficient synthetic route for the multistep Fe SCO in the cyanido-bridged framework which is a promising step toward rational design of advanced spin transition molecular switches.

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Source
http://pubs.acs.org/doi/10.1021/acs.inorgchem.9b00361
Publisher Site
http://dx.doi.org/10.1021/acs.inorgchem.9b00361DOI Listing
May 2019
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