Wiley, Chemistry - A European Journal, 11(17), p. 3038-3038, 2011
Wiley, Chemistry - A European Journal, 11(17), p. 3120-3127, 2011
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A novel bispyrazolylpyridine ligand incorporating lateral phenol groups, H(4) L, has led to an Fe(II) spin-crossover (SCO) complex, [Fe(H(4) L)(2) ][ClO(4) ](2) ⋅H(2) O⋅2 (CH(3) )(2) CO (1), with an intricate network of intermolecular interactions. It exhibits a 40 K wide hysteresis of magnetization as a result of the spin transition (with T(0.5) of 133 and 173 K) and features an unsymmetrical and very rich structure. The latter is a consequence of the coupling between the SCO and the crystallographic transformations. The high-spin state may also be thermally trapped, exhibiting a very large T(TIESST) (≈104 K). The structure of 1 has been determined at various temperatures after submitting the crystal to different processes to recreate the key points of the hysteresis cycle and thermal trapping; 200 K, cooled to 150 K and trapped at 100 K (high spin, HS), slowly cooled to 100 K and warmed to 150 K (low spin, LS). In the HS state, the system always exhibits disorder for some components (one ClO(4) (-) and two acetone molecules) whereas the LS phases show a relative ≈9 % reduction in the FeN bond lengths and anisotropic contraction of the unit cell. Most importantly, in the LS state all the species are always found to be ordered. Therefore, the bistability of crystallographic order-disorder coupled to SCO is demonstrated here experimentally for the first time. The variation in the cell parameters in 1 also exhibits hysteresis. The structural and magnetic thermal variations in this compound are paralleled by changes in the heat capacity as measured by differential scanning calorimetry. Attempts to simulate the asymmetric SCO behaviour of 1 by using an Ising-like model underscore the paramount role of dynamics in the coupling between the SCO and the crystallographic transitions.