We investigated by optical microscopy the thermal spin transition in single crystals of [Fe(bbtr)3](ClO4)2 (bbtr = 1,4-di(1,2,3-triazol-1-yl) butane). The growth of the low-spin phase was observed for different crystal orientations and sizes. The process always started from a corner of the crystal but its further development depended on the size, shape and thermal history of the crystal. In crystals of smaller size, under isothermal conditions, the low-spin phase developed in a continuous way, through the propagation of a rather well defined transformation front, with a higher propagation velocity inside the planes perpendicular to the c axis. In larger crystals the spontaneous occurrence of inhomogeneous stresses led to a stepwise propagation process.
  • Unidirectional Photoisomerization of Styrylpyridine for Switching the Magnetic Behavior of an Iron(II) Complex: A MLCT Pathway in Crystalline Solids
    A. Tissot, M.-L. Boillot, S. Pillet, E. Codjovi, K. Boukheddaden and L.M. Lawson Daku
    Journal of Physical Chemistry C, 114 (49) (2010), p21715-21722
    DOI:10.1021/jp106583f | unige:14853 | Abstract | Article HTML | Article PDF
The photoreactivity of two iron(II)−styrylpyridine frameworks Fe(stpy)4(NCSe)2 (stpy = 4-styrylpyridine) has been investigated for the very first time in a crystalline solid. A quantitative cis-to-trans isomerization of stilbenoids is shown to occur in the confined environment of the inorganic solid. The photochromic reaction was driven by a visible excitation into the metal-to-ligand charge transfer absorption of the high-spin all-cis complex. The solid-state transformation is accompanied by a unit-cell volume increase and an amorphization. Interestingly, the photoproduct formed by irradiating the high-spin all-cis reactant undergoes a spin conversion when the temperature is decreased. This observation is related to the “ligand-driven light-induced spin change” effect in a constrained environment.
  • Light-induced phase separation in the [Fe(ptz)6](BF4)2 spin-crossover single crystal
    F. Varret, K. Boukheddaden, C. Chong, A. Goujon, B. Gillon, J. Jeftic and A. Hauser
    Europhysics Letters, 77 (3) (2007), p30007
    DOI:10.1209/0295-5075/77/30007 | unige:3601 | Abstract | Article HTML | Article PDF
We present novel insight on like-spin domains (LSD) in cooperative spin transition solids by following the photo-transformation and the subsequent relaxation of a [Fe(ptz)6](BF4)2 single crystal in the vicinity of the light-induced instability. Self-organization under light is observed, accompanied by Barkhausen-like noise and jumps which reveal the presence of elastic interactions between LSDs. The light-induced phase separation process is discussed in terms of a dynamic potential providing spinodal instability in the corresponding temperature range. This useful concept is applicable to all types of switchable molecular solids.



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