A study of the soft X-ray photoreduction of [NiIV(S2CNEt2)3][BF4] and soft X-ray photoisomerisation of [PPh4][NiII(S2COEt)3] at the Ni L-edge †

Magnetic and electronic properties of RNiO3(R = Pr, Nd, Eu, Ho and Y) perovskites studied by resonant soft x-ray magnetic powder diffraction

“…Nevertheless, the energy position of the absorption edges depend strongly on coordination geometry, ligands and occupancies of the 3d shell. The shifts in energy for a valence change from Ni 2+ to Ni 4+ range from 1.4 eV (measured for pseudo-octahedral nickel dithiocarbamate and xanthate complexes) [39] to 2-3 eV predicted from electronic structure calculations [38,40]. The absorption edge energy position of RNiO 3 presented in figure 7 vary within 0.6 eV for the Ni L 3 and L 2 edges for different rare earth ions.…”

“…Furthermore, the left shoulder on the L 2 edge becomes more pronounced. Absorption spectra have proven to be useful experimental probes of changes of Ni valence [38,39]. Nevertheless, the energy position of the absorption edges depend strongly on coordination geometry, ligands and occupancies of the 3d shell.…”

A close look at dose: Toward L-edge XAS spectral uniformity, dose quantification and prediction of metal ion photoreduction

“…For [Co(acac) 3 ] at the Co XAS L-edge it is reported to be a factor of 2, while it is apparently absent for K 3 [Co(CN) 6 ] [69]. Also for Ni L-edge XAS of [Ni IV (S 2 CNR 2 ) 3 ][BF 4 ] type molecules [67], Mn L-edge XAS of Mn 12 -type single molecule magnets [71,73], N K-edge XAS of Fe 3+ [PhBP 3 ]-Fe N(p-tolyl) and [PhBP 3 tBu (pz')]Fe IV N(tBu) + [33], and Pt 4f XPS of [Pt(en)CI 4 ] [101] the dose-photoreduction relation is reported to be temperature-independent. For hydrocarbon bond breakage, e.g.…”

“…Detailed early work by Collison and Young [66][67][68][69] exists on molecular compounds studied at their V, Fe or Ni L-edges, after which a period of silence on the topic followed. Recently, however, awareness of this issue has increased, as is illustrated by Mn and Fe L-edge studies, mainly on single molecule magnets, in which radiation-induced chemistry is explicitly acknowledged to occur [33,[70][71][72][73][74][75][76].…”

Multiplet effects in X-ray spectroscopy

“…A number of 2p XAS studies on coordination compounds, including nickel dithiocarbamate complexes, vanadium with oxyoxime ligands and iron with bidentate N-donor ligands have been performed by the groups of Garner and co-workers [64][65][66]. An interesting study is on nickel dithiocarbamate and xanthate complexes, where it is shown that the 2p XAS experiments induce photoreduction of such nickel complexes, for example, modifying [Ni IV (S 2 CNEt 2 ) 3 ][BF 4 ] into a Ni II square-planar species.…”