Guest-Dependent Pressure-Induced Spin Crossover in FeII4[MIV(CN)8]2 (M=Mo,W) Cluster-Based Material Showing Persistent Solvent-Driven Structural Transformations |
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Authors: | Robert Jankowski Dr. Mateusz Reczyński Dr. Szymon Chorazy Mikołaj Zychowicz Mirosław Arczyński Dr. Marcin Kozieł Karolina Ogorzały Dr. Wacław Makowski Dr. Dawid Pinkowicz Prof. Dr. Barbara Sieklucka |
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Affiliation: | Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30387 Krakow, Poland |
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Abstract: | Discrete molecular species that can perform certain functions in response to multiple external stimuli constitute a special class of multifunctional molecular materials called smart molecules. Herein, cyanido-bridged coordination clusters {[FeII(2-pyrpy)2]4[MIV(CN)8]2} ⋅ 4 MeOH ⋅ 6 H2O (M=Mo ( 1 solv ), M=W ( 2 solv ) and 2-pyrpy=2-(1-pyrazolyl)pyridine are presented, which show persistent solvent driven single-crystal-to-single-crystal transformations upon sorption/desorption of water and methanol molecules. Three full desolvation–resolvation cycles with the concomitant change of the host molecules do not damage the single crystals. More importantly, the Fe4M2 molecules constitute a unique example where the presence of the guests directly affects the pressure-induced thermal spin crossover (SCO) phenomenon occurring at the FeII centres. The hydrated phases show a partial SCO with approximately two out-of-four FeII centres undergoing a gradual thermal SCO at 1 GPa, while in the anhydrous form the pressure-induced SCO effect is almost quenched with only 15 % of the FeII centres undergoing high-spin to low-spin transition at 1 GPa. |
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Keywords: | cluster compounds cyanides iron pressure-induced phase transitions sorption properties spin crossover |
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