J. W. Quilty

Photoemission study of temperature-induced and photoinduced spin-state transitions in spin-crossover complex [Fe(ptz)6](BF4)2

We report an x-ray photoemission spectroscopy study of spin-crossover complex [Fe(ptz) 6 ](BF 4 ) 2 (ptz = 1-propyltetrazole) to identify the electronic changes due to temperature-induced and photoinduced spin transitions. The energy difference between the Fe 2 p and F 1 s peaks is found to correlate with the low-spin (LS) to high-spin (HS) transition of [Fe(ptz) 6 ](BF 4 ) 2 . The Fe 2 p 3/2 spectrum of the HS state is accompanied by a charge-transfer satellite and is analyzed by configuration-interaction cluster-model calculations. Based on the electronic-structure parameters from the cluster-model analysis, the stability of the LS state against the HS state is calculated as a function of the Fe–N bond length. A drastic bond-length reduction is required to stabilize the LS state and is also related to the observed core-level shift. The postillumination spectral shape well reproduces the spectrum before the laser illumination, suggesting that the surface of the Fe complex is chemically stable against the...