American Chemical Society, Inorganic Chemistry, 6(56), p. 3144-3148, 2017
DOI: 10.1021/acs.inorgchem.7b00071
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The Fe[BF₄]₂ complex of the Schiff base podand tris[4-(thiazol-4-yl)-3-aza-3-butenyl]amine exhibits gradual thermal spin-crossover with T₁⁄₂ ≈ 208 K in the solid state. A weak discontinuity in the magnetic susceptibility curve at 190 K is associated with a reentrant symmetry-breaking transition involving a trebling of the unit cell volume (from P2₁/c, Z = 4, to P2₁, Z = 12). The intermediate phase contains six independent cations in puckered layers of low-spin, and high-spin or mixed-spin, molecules with an overall 30% high-spin population at 175 K.