Capel Berdiell, I orcid.org/0000-0003-3828-7097, Hochdörffer, T, Desplanches, C orcid.org/0000-0001-8524-3690 et al. (8 more authors) (2019) Supramolecular Iron Metallocubanes Exhibiting Site-Selective Thermal and Light-Induced Spin-Crossover. Journal of the American Chemical Society, 141 (47). pp. 18759-18770. ISSN 0002-7863
Abstract
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 twelve 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 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, 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 re-actions 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.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | Copyright © American Chemical Society. This is an author produced version of a paper published in the Journal of the American Chemical Society. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Inorganic Chemistry (Leeds) The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Organic Chemistry (Leeds) The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Physics and Astronomy (Leeds) > Condensed Matter (Leeds) The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) |
Funding Information: | Funder Grant number EPSRC (Engineering and Physical Sciences Research Council) EP/K012568/1 Leverhulme Trust RPG-2015-095 EPSRC (Engineering and Physical Sciences Research Council) EP/K00512X/1 |
Depositing User: | Symplectic Publications |
Date Deposited: | 06 Nov 2019 15:26 |
Last Modified: | 17 Dec 2024 15:13 |
Status: | Published |
Publisher: | American Chemical Society |
Identification Number: | 10.1021/jacs.9b08862 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:153161 |