Kulmaczewski, R orcid.org/0000-0002-3855-4530, Trzop, E orcid.org/0000-0003-1998-1825, Collet, E orcid.org/0000-0003-0810-7411 et al. (2 more authors) (2020) Structure:Function Relationships for Thermal and Light-Induced Spin-Crossover in Isomorphous Molecular Materials. Journal of Materials Chemistry C. D0TC02174A. ISSN 2050-7526
Abstract
Isomorphous [FeL2][BF4]2·solv and [FeL2][ClO4]2·solv (L = 4-{isopropylsulfanyl}-2,6-di{pyrazol-1-yl}pyridine; solv = MeNO2, MeCN, 0.67Me2CO or H2O) exhibit a variety of thermal spin-crossover (SCO) behaviours. This complexity extends to the light induced excited spin state trapping (LIESST) experiment where, uniquely, five members show the expected inverse relationship between their thermal SCO (T½) and LIESST relaxation (T(LIESST)) temperatures but a sixth compound ([FeL2][BF4]2·MeCN) does not. The structural basis of these observations has been probed by X-ray crystallography, photocrystallography and periodic DFT+U+D2 calculations. Among the compounds examined, more cooperative thermal SCO is strongly coupled to order/disorder transitions in the solvent and/or isopropyl substituents and vice versa. A series of symmetry breaking phase transitions in [FeL2][BF4]2·MeNO2, before and after photoexcitation, occurs 10-20 K below T(LIESST) and has no direct bearing on the T½/T(LIESST) relationship. These phase changes are not shown by other compounds in the study. The anomalous T(LIESST) in [FeL2][BF4]2·MeCN, and its observed negative lattice expansion during isothermal low→high-spin conversion, are not reproduced computationally which implies those properties are unconnected to its spin state energetics. Its minimised high- and low-spin structures also deviate more from experiment than the other compounds investigated, in the most plastic region of the lattice which includes the solvent molecule. We conclude that reorientation of the linear MeCN molecule contributes a temperature-dependent lattice activation barrier to the spin-transition in [FeL2][BF4]2·MeCN, leading to the higher T(LIESST) value observed.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © Royal Society of Chemistry 2020. This is an author produced version of an article published in Journal of Materials Chemistry C. 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) |
Funding Information: | Funder Grant number EPSRC (Engineering and Physical Sciences Research Council) EP/K012568/1 |
Depositing User: | Symplectic Publications |
Date Deposited: | 02 Jun 2020 15:23 |
Last Modified: | 20 Dec 2024 12:52 |
Status: | Published online |
Publisher: | Royal Society of Chemistry |
Identification Number: | 10.1039/d0tc02174a |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:161210 |