Spectral Signatures of Ultrafast Spin Crossover in Single Crystal [FeII(bpy)3](PF6)2 |
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| Authors: | Ryan Field Lai Chung Liu Dr Wojciech Gawelda Dr Cheng Lu Dr R J Dwayne Miller |
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| Institution: | 1. Departments of Chemistry and Physics, University of Toronto, Toronto, ON, Canada;2. The Hamburg Centre for Ultrafast Imaging, Centre for Free Electron Laser Science, Max Planck Institute for the Structure and Dynamics of Matter, Hamburg, Germany;3. European XFEL, Hamburg, Germany |
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| Abstract: | Solvated iron(II)‐tris(bipyridine) (FeII(bpy)3]2+) has been extensively studied with regard to the spin crossover (SCO) phenomenon. Herein, the ultrafast spin transition dynamics of single crystal FeII(bpy)3](PF6)2 was characterized for the first time using femtosecond transient absorption (TA) spectroscopy. The single crystal environment is of interest for experiments that probe the nuclear motions involved in the SCO transition, such as femtosecond X‐ray and electron diffraction. We found that the TA at early times is very similar to what has been reported in solvated FeII(bpy)3]2+, whereas the later dynamics are perturbed in the crystal environment. The lifetime of the high‐spin state is found to be much shorter (100 ps) than in solution due to chemical pressure exerted by the lattice. Oscillatory behavior was observed on both time scales. Our results show that single crystal FeII(bpy)3](PF6)2 serves as an excellent model system for localized molecular spin transitions. |
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| Keywords: | charge transfer electron-phonon coupling iron spin crossover time-resolved spectroscopy |
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