Dissemin is shutting down on January 1st, 2025

Published in

Wiley, Chemistry - A European Journal, 11(17), p. 3038-3038, 2011

DOI: 10.1002/chem.201190050

Wiley, Chemistry - A European Journal, 11(17), p. 3120-3127, 2011

DOI: 10.1002/chem.201003197

Links

Tools

Export citation

Search in Google Scholar

Coupled Crystallographic Order-Disorder and Spin State in a Bistable Molecule: Multiple Transition Dynamics

This paper is available in a repository.
This paper is available in a repository.

Full text: Download

Green circle
Preprint: archiving allowed
Orange circle
Postprint: archiving restricted
Red circle
Published version: archiving forbidden
Data provided by SHERPA/RoMEO

Abstract

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 FeN 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.