Pask, C.M. orcid.org/0000-0002-2241-5069, Kulak, A.N. orcid.org/0000-0002-2798-9301 and Halcrow, M.A. orcid.org/0000-0001-7491-9034 (Accepted: 2024) Structural Consequences of Different Metal Compositions in the Doped Spin‐Crossover Crystals [FezM1−z(bpp)2][BF4]2 (M = Ni, Zn; bpp = 2,6‐Bis{pyrazol‐1‐yl}pyridine). European Journal of Inorganic Chemistry. ISSN 1434-1948 (In Press)
Abstract
Variable temperature crystallographic characterization of [FezZn1‒z(bpp)2][BF4]2 (bpp = 2,6‐bis{pyrazol‐1‐yl}pyridine; z = 0.88, 0.72 and 0.27) and [FezNi1‒z(bpp)2][BF4]2 (z = 0.83, 0.72 and 0.32) is presented. Comparison with previously published data confirms the isothermal unit cell volume change during spin‐crossover (ΔVSCO) behaves differently in the Zn‐ and Ni‐doped crystals. For the FeZn crystals, the relationship between ΔVSCO and z is continuous for z ≥ 0.3 but is steeper than expected, so ΔVSCO ≈ 0 for z = 0.27. In contrast ΔVSCO in the FeNi materials shows only a small variation between 0.83 ≥ z ≥ 0.46, before decreasing more strongly at higher dilution. ΔVSCO in each FeZn crystal is smaller than for its FeNi analogue with a similar composition. As well as the dopant ion ionic radius, the smaller ΔVSCO for the Zn‐doped materials reflects their T½ values, which are lower than for their FeNi counterparts. The contribution of T½ to this behavior is especially evident at high metal dilution.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Keywords: | Iron; N ligands; Spin-crossover; Solid solution; Crystal engineering |
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) |
Depositing User: | Symplectic Publications |
Date Deposited: | 24 Jul 2024 14:04 |
Last Modified: | 20 Mar 2025 14:52 |
Status: | In Press |
Publisher: | Wiley |
Identification Number: | 10.1002/ejic.202400334 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:215079 |