Single-Crystal to Single-Crystal Transformation of a Spin-Crossover Hybrid Perovskite via Thermal-Induced Cyanide Linkage Isomerization.
Wei-Wei WuKai-Ping XieGuo-Zhang HuangZe-Yu RuanYan-Cong ChenSi-Guo WuZhao-Ping NiMing-Liang TongPublished in: Inorganic chemistry (2022)
Linkage isomers involving changes in the bonding mode of ambidentate ligands have potential applications in data storage, molecular machines, and motors. However, the observation of the cyanide-linkage-isomerism-induced spin change (CLIISC) effect characterized by single-crystal X-ray diffraction remains a considerable challenge. Meanwhile, the high-spin and low-spin states can be reversibly switched in spin-crossover (SCO) compounds, which provide the potential for applications to data storage, switches, and sensors. Here, a new perovskite-type SCO framework (PPN)[Fe{Ag(CN) 2 } 3 ] (PPN + = bis(trisphenylphosphine)iminium cation) is synthesized, which displays the unprecedented aging and temperature dependences of hysteretic multistep SCO behaviors near room temperature. Moreover, the thermal-induced cyanide linkage isomerization from Fe II -N≡C-Ag I to Fe II -C≡N-Ag I is revealed by single-crystal X-ray diffraction, Raman, and Mössbauer spectra, which is associated with a transition from the mixed spin state to the low-spin state and a dramatic volume shrinkage. Considering the wide use of cyanogen in magnetic systems, the association of CLIISC and SCO opens a new dimension to modulate the spin state and realize a colossal negative thermal expansion.
Keyphrases
- room temperature
- ionic liquid
- density functional theory
- single molecule
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- randomized controlled trial
- visible light
- machine learning
- transition metal
- molecular dynamics
- computed tomography
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- hepatitis c virus
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- aqueous solution
- crystal structure
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- placebo controlled