Journal
INORGANIC CHEMISTRY
Volume 47, Issue 17, Pages 7577-7587Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic8002977
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Funding
- European Union
- CEFIPRA [IFC 3408-3]
- Spanish MEC [MAT2004-03395-C02-02]
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The title compound [Fe-II(L)(2)][ClO4](2) center dot C7H8 (L = 2-[3-(2'-pyridyl)pyrazol-1-ylmethyl]pyridine) has been isolated while attempting to grow single crystals of the spin-transition (continuous-type) compound [Fe-II (L)(2)][ClO4](2), published earlier (Dalton Trans. 2003, 3392-3397). Magnetic susceptibility measurements, as well as Mossbauer and calorimetric investigations on polycrystalline samples of [Fe(L)(2)][ClO4](2) center dot C7H8 revealed the occurrence of an abrupt HS (T-5(2)) <-> LS ((1)A(1)) transition with steep and narrow (2 K) hysteresis at similar to 232 K The photomagnetic properties exhibit features typical for a broad distribution of activation energies, with relaxation curves in the shape of stretched exponentials. We performed a crystal structure determination of the compound at 120, 240, and 270 K. A noteworthy temperature-dependent behavior of the structural parameters was observed, in terms of disorder of both the anions and solvent molecules, leading to a strong thermal dependence of the strength and dimensionality of the interaction network. Additional data were obtained by diffuse reflectance measurements. We model and discuss the antagonistic effects of interactions and disorder by using a two-level cooperative mean-field approach which includes a distribution of barrier energies at the microscopic scale.
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