Supramolecular iron metallocubanes exhibiting site-selective thermal and light-induced spin-crossover
| Autor: | Rafal Kulmaczewski, Malcolm A. Halcrow, Juliusz A. Wolny, Tim Hochdörffer, Izar Capel Berdiell, Namrah Shahid, Cédric Desplanches, Volker Schünemann, Oscar Cespedes, Stuart L. Warriner, Guillaume Chastanet |
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| Přispěvatelé: | School of Chemistry [Leeds], University of Leeds, Department of Physics, Technical University of Kaiserslautern (TU Kaiserslautern), Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), School of Physics and Astronomy [Leeds], This work was funded by the Leverhulme Trust (RPG-2015-095), the EPSRC (EP/K012568/1, EP/K00512X/1) and the COST network CM1305 Explicit Control of Spin States in Technology and Biology (ECOSTBio). We thank Diamond Light Source for access to beamline I19 (MT10334), which contributed to the results presented here. The Aquitaine Region is acknowledged for the development of the International Center of Photomagnetism in Aquitaine (ICPA) platform. V.S. acknowledges the support of the German Research Foundation (DFG) through the Transregional Collaborative Research Center SFB/TRR173 Spin+X and the German Ministry of Research (BMBF) under 05K16UKA. |
| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
Hydrogen bond
Supramolecular chemistry General Chemistry [CHIM.MATE]Chemical Sciences/Material chemistry 010402 general chemistry 01 natural sciences Biochemistry Magnetic susceptibility Catalysis LIESST 0104 chemical sciences 3. Good health chemistry.chemical_compound Crystallography Colloid and Surface Chemistry chemistry Cubane Spin crossover Mössbauer spectroscopy Moiety |
| Zdroj: | Journal of the American Chemical Society Journal of the American Chemical Society, American Chemical Society, 2019, 141 (47), pp.18759-18770. ⟨10.1021/jacs.9b08862⟩ |
| ISSN: | 0002-7863 1520-5126 |
| Popis: | International audience; Treatment of Fe[BF4]2·6H2O with 4,6-di(pyrazol-1-yl)-1H-pyrimid-2-one (HL1) or 4,6-di(4-methylpyrazol-1-yl)-1H-pyrimid-2-one (HL2) affords solvated crystals of [{FeIII(OH2)6}⊂FeII8(μ-L)12][BF4]7 (1, HL = HL1; 2, HL = HL2). The centrosymmetric complexes contain a cubic arrangement of iron(II) centers, with bis-bidentate [L]− ligands bridging the edges of the cube. The encapsulated [Fe(OH2)6]3+ moiety templates the assembly through 12 O–H···O hydrogen bonds to the [L]− hydroxylate groups. All four unique iron(II) ions in the cages are crystallographically high-spin at 250 K, but they undergo a gradual high → low spin-crossover on cooling, which is predominantly centered on one iron(II) site and its symmetry-related congener. This was confirmed by magnetic susceptibility data, light-induced excited spin state trapping (LIESST) effect measurements, and, for 1, Mössbauer spectroscopy and diffuse reflectance data. The clusters are stable in MeCN solution, and 1 remains high-spin above 240 K in that solvent. The cubane assembly was not obtained from reactions using other iron(II) salts or 4,6-di(pyrazol-1-yl)pyrimidine ligands, highlighting the importance of hydrogen bonding in templating the cubane assembly. |
| Databáze: | OpenAIRE |
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