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 (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, 27 (28). e202400334. ISSN 1434-1948
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 T1/2 values, which are lower than for their FeNi counterparts. The contribution of T1/2 to this behavior is especially evident at high metal dilution.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2024 The Authors. This is an open access article under the terms of the Creative Commons Attribution License (CC-BY 4.0), which permits unrestricted use, distribution and reproduction in any medium, provided the original work is properly cited. |
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: | 07 Apr 2025 13:00 |
Status: | Published |
Publisher: | Wiley |
Identification Number: | 10.1002/ejic.202400334 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:215079 |