We present an advanced material exhibiting a spin crossover (SCO) effect generated by the combined application of two external stimuli, temperature and chemical treatment related to the crystallization solvent exchange. The reported material is based on a bimetallic {[FeII(4-Brphpy)4]3[ReV(CN)8]2}⋅7MeOH [1, 4-Brphpy = 4-(4-bromophenyl)pyridine] coordination network built of cyanido-bridged layers and interstitial methanol molecules. A weakly bonded solvent can be exchanged into the water, which results in a hydrated phase, {[FeII(4-Brphpy)4]3[ReV(CN)8]2}⋅5H2O (1-hyd). The difference in solvent content between 1 and 1-hyd is sufficient to induce a remarkable change in spin transition properties. Despite the {N6} coordination environment around Fe(II), 1 reveals a stable high-spin state in the whole 2–300 K temperature range, which was assigned to the stiffening of the framework due to a series of non-covalent interactions involving solvent and 4-Brphpy ligands. Upon the exchange of solvent to water, the framework of 1-hyd becomes more flexible producing a thermally induced SCO effect, which occurs in two distinguishable steps in the broad 70–250 K range. The 1 to 1-hyd transformation can be reversed by immersion in the original solvent, thus, the chemical ON–OFF switching of a thermal SCO effect was achieved. This work shows that solvent exchange processes within bimetallic layered FeII–[ReV(CN)8]3– networks give an efficient route for reversible chemical modulation of thermally induced SCO properties.
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14 April 2021
Research Article|
April 12 2021
The ON–OFF switching of thermal spin crossover by interstitial solvent exchange in a layered ReV–CN–FeII coordination framework
Special Collection:
Spin Transition Materials: Molecular and Solid-State
Tomasz Charytanowicz
;
Tomasz Charytanowicz
1
Faculty of Chemistry, Jagiellonian University
, Gronostajowa 2, 30-387 Krakow, Poland
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Jakub J. Zakrzewski
;
Jakub J. Zakrzewski
1
Faculty of Chemistry, Jagiellonian University
, Gronostajowa 2, 30-387 Krakow, Poland
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Katarzyna Dziedzic-Kocurek
;
Katarzyna Dziedzic-Kocurek
2
Marian Smoluchowski Institute of Physics, Jagiellonian University
, Łojasiewicza 11, 30-348 Krakow, Poland
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Szymon Chorazy
;
Szymon Chorazy
a)
1
Faculty of Chemistry, Jagiellonian University
, Gronostajowa 2, 30-387 Krakow, Poland
a)Authors to whom correspondence should be addressed: chorazy@chemia.uj.edu.pl and barbara.sieklucka@uj.edu.pl
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Barbara Sieklucka
Barbara Sieklucka
a)
1
Faculty of Chemistry, Jagiellonian University
, Gronostajowa 2, 30-387 Krakow, Poland
a)Authors to whom correspondence should be addressed: chorazy@chemia.uj.edu.pl and barbara.sieklucka@uj.edu.pl
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a)Authors to whom correspondence should be addressed: chorazy@chemia.uj.edu.pl and barbara.sieklucka@uj.edu.pl
Note: This paper is part of the Special Topic on Spin Transition Materials: Molecular and Solid-State.
J. Appl. Phys. 129, 143902 (2021)
Article history
Received:
February 02 2021
Accepted:
March 28 2021
Citation
Tomasz Charytanowicz, Jakub J. Zakrzewski, Katarzyna Dziedzic-Kocurek, Szymon Chorazy, Barbara Sieklucka; The ON–OFF switching of thermal spin crossover by interstitial solvent exchange in a layered ReV–CN–FeII coordination framework. J. Appl. Phys. 14 April 2021; 129 (14): 143902. https://doi.org/10.1063/5.0046296
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