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.
  • Spin-transition in nearly cubic site in [FeII(L)3][PF6]2
    V. Mishra, R. Mukherjee, J. Linares, E. Codjovi, F. Varret and L.M. Lawson Daku
    Hyperfine Interactions, 188 (1-3) (2009), p71-78
    DOI:10.1007/s10751-008-9891-6 | unige:3560 | Abstract | Article PDF
 
The spin-transition (1A15T2) behaviour of a new mononuclear iron(II) compound [FeII(L)3][PF6]2[L = 2-[3-(2′-pyridyl)pyrazole-1-ylmethyl]pyridine] has been investigated by 57Fe Mössbauer spectroscopy. Analysis of the Mössbauer spectra revealed low value of the quadrupole splitting of the high-spin state which reflects iron(II) to be in nearly cubic lattice site. Mössbauer spectra under light show the light-induced excited spin state trapping effect and the observed quadrupole splitting of the metastable high-spin state is found little sensitive to the high-spin fraction value. DFT calculations are in progress to document the almost cubic nature of the ligand-field acting on the iron atom.
  
  • 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.
  • Quasi-static nature of the light induced thermal hysteresis in [Fe(ptz)6](BF4)2 spin-transition solid
    J. Jeftic, M. Matsarski, A. Hauser, A. Goujon, E. Codjovi, J. Linares and F. Varret
    Polyhedron, 20 (11-14) (2001), p1599-1606
    DOI:10.1016/S0277-5387(01)00660-X | unige:3510 | Abstract | Article HTML | Article PDF
 
The quasi-static nature of a light induced thermal hysteresis was studied on the spin-transition compound [Fe(ptz)6](BF4)2, by means of optical spectroscopy and magnetic measurements in the temperature interval between 10 and 80 K. Various experimental procedures are discussed in relation to the competition between the two processes considered, namely the photoexitation and the high-spin→low-spin relaxation. A detailed discussion of the experimental parameters, which should be considered in order to avoid erroneous interpretations of LITH, is given.
Present paper is an overview of our efforts during the past few years to understand complicated corelations of physical phenomena related to pressure in Fe(I1) solid state spin transition systems. Some principal results concerning p, T, λ-experiments are extracted. In the context of correlation of the crystallographic phase transition with simultaneous HS LS relaxation and LS HS photopopulation, we show the latest results: Brillouin and magnetic measurements on the crystal [Fe(pt6](BF6)2.
The propagation of the high-spin (HS) → low-spin (LS) relaxation at 53 K in a single crystal of the iron (II) spin-crossover compound [Fe(ptz)6](BF4)2 was followed by photography, after inducing the local photoexcitation to the metastable HS state at 20 K using the single wavelength (457 nm Ar± ion laser) irradiation. The photoinduced formation of the HS—LS patterns with a characteristic diameter of some 0.1 mm was observed to occur inhomogeneously at a macroscopic scale already during photoexcitation. The contrast between the HS (transparent) and the LS (purple) regions was amplified during relaxation. The effect is described in terms of a transient instability, for which a microscopic model in the mean-field approximation is proposed. The mechanism for the development of patterns at the macroscopic scale is discussed.

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