2021
DOI: 10.1021/acs.chemmater.1c03143
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Cooperativity and Metal–Linker Dynamics in Spin Crossover Framework Fe(1,2,3-triazolate)2

Abstract: Cooperative interactions are responsible for the useful properties of spin crossover (SCO) materialslarge hysteresis windows, critical temperatures near room temperature, and abrupt transitionswith hybrid framework materials exhibiting the greatest cooperativity and hysteresis of all SCO systems. However, little is known about the chemical origin of cooperativity in frameworks. Here, we present a combined experimental−computational approach for identifying the origin of cooperativity in the metal−organic fra… Show more

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Cited by 24 publications
(32 citation statements)
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“…Consistent with UiO-66 being chemically robust, it possesses larger flexibility constants and larger endothermic enthalpy barriers than reported previously for CuBTC or M(1,2,3-triazolate) 2 MOFs. 7,8 And yet, a ln X of 1.84 is lower than stability constants reported for coordination polymers, including metal–carbene and metal–pyridyl materials known to exhibit self-healing behavior. 20,21 As reference, a table of stability constants for these materials is provided in the ESI,† Table S4).…”
mentioning
confidence: 78%
“…Consistent with UiO-66 being chemically robust, it possesses larger flexibility constants and larger endothermic enthalpy barriers than reported previously for CuBTC or M(1,2,3-triazolate) 2 MOFs. 7,8 And yet, a ln X of 1.84 is lower than stability constants reported for coordination polymers, including metal–carbene and metal–pyridyl materials known to exhibit self-healing behavior. 20,21 As reference, a table of stability constants for these materials is provided in the ESI,† Table S4).…”
mentioning
confidence: 78%
“…S16), suggesting that higher temperatures suppress the intercalation of BF4anions into the Fe(TA)2 nanopores. A possible contributing factor could be that enhanced metal-ligand dynamic bonding at elevated temperatures 46,47 might induce additional phonon scattering that interferes with BF4intercalation.…”
Section: Redox Entropy Of Anion Intercalation Within Nanoconfined Fe(...mentioning
confidence: 99%
“… 17 A detailed investigation of this unique compound attributed the origin of the behavior to the combination of a rigid lattice and ionic polarizable bonds due to the bridging triazolate ligands. 22 For less symmetric discrete Fe II compounds with meridional tridentate ligands exhibiting reproducible hysteresis exceeding 100 K 16 , 23 , 24 ( Scheme 1 ), the underlying structural mechanisms of the bistability remain unknown. Namely, the exceptional chemical variability of the tridentate ligands offers attractive prospects for tuning the transition temperature to the desired operating range.…”
Section: Introductionmentioning
confidence: 99%
“…The only fully structurally characterized compound with the hysteresis >100 K is a 3D polymeric complex [Fe II (1,2,3-triazolate) 2 ] 0 (Δ T h = 110 K), which undergoes ST with an outstandingly large and highly symmetric variation of the lattice (cubic → cubic) . A detailed investigation of this unique compound attributed the origin of the behavior to the combination of a rigid lattice and ionic polarizable bonds due to the bridging triazolate ligands . For less symmetric discrete Fe II compounds with meridional tridentate ligands exhibiting reproducible hysteresis exceeding 100 K ,, (Scheme ), the underlying structural mechanisms of the bistability remain unknown.…”
Section: Introductionmentioning
confidence: 99%