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Pressure‐Induced Spin Crossover at Room Temperature in a Nanoporous Host‐Guest Framework Structure
Author(s) -
Vatsha Banele,
Goliath Rowan,
Hearne Giovanni
Publication year - 2021
Publication title -
chempluschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.801
H-Index - 61
ISSN - 2192-6506
DOI - 10.1002/cplu.202000557
Subject(s) - spin crossover , molecule , nanoporous , chemistry , spin (aerodynamics) , ion , metal organic framework , metal , spin states , chemical physics , crystallography , inorganic chemistry , thermodynamics , adsorption , organic chemistry , physics
The two‐dimensional (2D) metal‐organic framework compound Fe 2 (azpy) 4 (NCS) 4 (azpy=trans‐4,4′‐azopyridine, NCS=thiocyanate) has been pressurized in isopropanol and ethanol that act as guest molecules and pressure‐transmitting media. Room temperature conversion of metal‐ion sites from high‐spin to low‐spin states under high‐pressure‐driven uptake of guest molecules was investigated. Upon isopropanol guest inclusion, spin conversion of ∼66 % low‐spin abundance is attained by ∼3 GPa. Spin‐crossover progression stimulated by ethanol guest inclusion is more sluggish and ∼56 % low‐spin abundance is attained by ∼5.5 GPa. This pressure‐facilitated guest‐specific triggering of spin crossover is suggestive of guest‐molecule interactions with the local coordination network of the Fe(II) core, which increases the ligand field. Appreciable low‐spin abundances attained at room temperature upon pressurization, are comparable to maximal ∼50 % spin conversions only attainable below ∼150 K at ambient pressure.