期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 18, 期 19, 页码 5924-5934出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201102637
关键词
iron; ligand effects; photomagnetism; spin crossover; X-ray diffraction
资金
- PHC ALLIANCE
A comprehensive study of the magnetic and photomagnetic behaviors of cis-[Fe(picen)(NCS)2] (picen=N,N'-bis(2-pyridylmethyl)1,2-ethanediamine) was carried out. The spin-equilibration was extremely slow in the vicinity of the thermal spin-transition. When the cooling speed was slower than 0.1 K?min-1, this complex was characterized by an abrupt thermal spin-transition at about 70 K. Measurement of the kinetics in the range 6070 K was performed to approach the quasi-static hysteresis loop. At low temperatures, the metastable HS state was quenched by a rapid freezing process and the critical T(TIESST) temperature, which was associated with the thermally induced excited spin-state-trapping (TIESST) effect, was measured. At 10 K, this complex also exhibited the well-known light-induced excited spin-state-trapping (LIESST) effect and the T(LIESST) temperature was determined. The kinetics of the metastable HS states, which were generated from the freezing effect and from the light-induced excitation, was studied. Single-crystal X-ray diffraction as a function of speed-cooling and light conditions at 30 K revealed the mechanism of the spin-crossover in this complex as well as some direct relationships between its structural properties and its spin state. This spin-crossover (SCO) material represents a fascinating example in which the metastability of the HS state is in close vicinity to the thermal spin-transition region. Moreover, it is a beautiful example of a complex in which the metastable HS states can be generated, and then compared, either by the freezing effect or by the LIESST effect.
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