An ESCA investigation of some copper complexes

Insight into Organometallic Intermediate and Its Evolution to Covalent Bonding in Surface-Confined Ullmann Polymerization

“…57 The binding energy (BE) shifts of the Br 3d 5/2 core level (Figure 4) reflect the difference between bromine atoms linked to the phenyl ring (at LT, BE = 70.9 eV) 60 and to the copper substrate (at RT, BE = 68.4 eV and at 500 K, BE = 68.5 eV). 61 The weaker low-BE component of Br 3d at LT is due to damage from the incident beam, which causes dehalogenation (see Figure S3 in Supporting Information). At RT, the weaker high-BE component of Br 3d probably originates from one of the two distinct chemical environments of Br atoms.…”

Reply to “Comment on ‘Insight into Organometallic Intermediate and Its Evolution to Covalent Bonding in Surface-Confined Ullmann Polymerization’”

“…Br 3d and Br 3p Levels. We presented chemical shifts of Br 3d spectra in our paper 1 and referred to the work by Folkesson et al 12 However, that work reports data based on Br 3p spectra. The Comment is correct in that the reference is not appropriate for Br 3d: more suitable references are the work of Vasquez, 13 where the correct value for CuÀBr in Br 3d can be found, and the article of Krasnikov et al, 14 for the corresponding CÀBr value.…”

Comment on “Insight into Organometallic Intermediate and Its Evolution to Covalent Bonding in Surface-Confined Ullmann Polymerization”

“…Besides this, it is surprising to see such a clear Br 3d spectrum since it sits so close the Cu 3p region (binding energy around 75 eV). The background or satellite from the copper substrate can be very strong to bury the tiny Br 3d signal; therefore, the Br 3p peak was usually chosen instead to avoid such overlap, as reported in the previous paper . Meanwhile, the authors also used this reference to explain the modified state of Br 3d where the bromine was supposed to be linked to the copper substrate both at RT and 500 K. Interestingly, as mentioned before, no single Br 3d peak was measured or discussed by Folkesson et al in their work, but instead, the Br 3p peak was intensively investigated by them.…”

“…The background or satellite from the copper substrate can be very strong to bury the tiny Br 3d signal; therefore, the Br 3p peak was usually chosen instead to avoid such overlap, as reported in the previous paper . Meanwhile, the authors also used this reference to explain the modified state of Br 3d where the bromine was supposed to be linked to the copper substrate both at RT and 500 K. Interestingly, as mentioned before, no single Br 3d peak was measured or discussed by Folkesson et al in their work, but instead, the Br 3p peak was intensively investigated by them. Moreover, the authors introduced the explanation for the Br 3d spectrum taken at RT by saying that the weaker, higher binding energy component of Br 3d probably comes from one of the two distinct chemical environments of Br atoms; however, when looking at the STM measurements or density functional theory (DFT) simulated model (from Figure 3), one can easily figure out that these two distinct chemical bromine atoms hold roughly equal quantity with respect to each other.…”