Wavelength selective light-induced magnetic effects in the binuclear spin crossover compound {[Fe(bt)(NCS)_2]_2(bpym)}

摘要

Using Fourier transform infrared spectroscopy, x-ray diffraction, and magnetic susceptibility measurements under light irradiation, the selective light-induced excited spin state trapping (LIESST) and the reversible-LIESST effect have been evidenced and studied in depth in the binuclear spin crossover compound {[Fe(bt) ×(NCS)_2]_2bpym}. In this system, each magnetic site can switch from low spin (LS) to high spin (HS), so that three states exist, namely, the LS-LS, HS-LS, and HS-HS. All these techniques shine a new light on the high phototunability of this system. In addition to the direct photoswitching from the LS-LS to the HS-LS or to the HS-HS state, here we show that photoinduced switching between the excited photoinduced states can be triggered in a reversible way: from HS-LS to HS-HS (irradiation around 800 nm), or reverse from HS-HS to HS-LS (irradiation around 1300 nm). The nature of the intermediate HS-LS state during the thermal and light-induced spin state changes is also discussed by comparing the spectroscopic measurements and the structural analysis. The loss of inversion symmetry in the HS-LS molecular state, where the two magnetic Fe sites are no more equivalent, is not accompanied by any long-range ordering of the noncentrosymmetric molecules in the crystal. Therefore the continuous double-step spin conversion corresponds to a double crossover.