Thin film iron-tetracyanoethylene Fe(TCNE)x, x ~ 2, as determined by photoelectron spectroscopy, was grown in situ under ultra-high vacuum conditions using a recently developed physical vapor deposition-based technique for fabrication of oxygen- and precursor-free organicbased molecular magnets. Photoelectron spectroscopy results show no spurious trace elements in the films, and the iron is of Fe²+ valency. The highest occupied molecular orbital of Fe(TCNE)x is located at ~1.7 eV vs. Fermi level and is derived mainly from the TCNE− singly occupied molecular orbital according to photoelectron spectroscopy and resonant photoelectron spectroscopy results. The Fe(3d)- derived states appear at higher binding energy, ~4.5 eV, which is in contrast to V(TCNE)2 where the highest occupied molecular orbital is mainly derived from V(3d) states. Fitting ligand field multiplet and charge transfer multiplet calculations to the Fe L-edge near edge X-ray absorption fine structure spectrum yields a high-spin Fe²+ (3d6) configuration with a crystal field parameter 10Dq ~ 0.6 eV for the Fe(TCNE)x system. We propose that the significantly weaker Fe-TCNE ligand interaction as compared to the room temperature magnet V(TCNE)2 (10Dq ~ 2.3 eV) is a strongly contributing factor to the substantially lower magnetic ordering temperature (TC) seen for Fe(TCNE)x - type magnets.
|Number of pages||8|
|Journal||Applied physics A: Materials science and processing|
|Publication status||Published - 19 Dec 2008|
- SMI-NE: From 2006 in EWI-NE
Bhatt, P., Carlegrim, E., Kanciurzewska, A., de Jong, M. P., & Fahlman, M. (2008). Electronic structure of thin film iron-tetracyanoethylene: Fe(TCNE)x. Applied physics A: Materials science and processing, 95(131), 131-138. [10.1007/s00339-008-5032-y]. https://doi.org/10.1007/s00339-008-5032-y