0000000000267207
AUTHOR
Delphine Cabaret
A Study Using X-ray Absorption and Emission Spectroscopy of Dioxygen-Binding Xerogels Incorporating Cyclam Units Complexed with Copper Salts.
X-ray absorption spectroscopy was used to elucidate how hybrid xerogels complexed with CuCl2 could reversibly bind molecular dioxygen. Difference EXAFS analyses at the Cu K-edge suggest that dioxygen could bridge two Cu atoms in a μ-η1:η1 peroxo-like conformation with unequal Cu···O distances. Only the short distance (RCu–O1 = 1.86 ± 0.01 A) was unambiguously determined and looks typical of a CuII site. The Cu···Cu internuclear distances would be rather long: RCu–Cu ≈ 4.0 A (3.9 A) for the oxygenated (oxygen-free) xerogels. Cl K-edge EXAFS spectra revealed the pre-existence in the oxygen-free xerogels of CuI sites with short Cl–Cu bonds (2.11 ± 0.03 A). Pentacoordinate CuII sites with a lon…
Structure of Dioxygen Binding Xerogels Incorporating Cyclams Complexed with CuCl2 Salts
X-ray absorption/emission spectroscopies were combined in order to elucidate how hybrid xerogels complexed with CuCl2 could bind reversibly O2. Difference EXAFS analyses at the Cu K-edge revealed the existence of binuclear structures with long Cu...Cu distances, i.e. RCu–Cu ≈ 3.98 A and 3.87 A for the oxygenated and oxygen-free xerogels. In oxygenated xerogels, dioxygen would bridge two Cu atoms in a μ-η1 : η1 peroxo-like conformation. The Cu-O signal found at short distance (RCu−O1 = 1.85 ± 0.01 A) is fully consistent with 40% of O2 molecules being chemisorbed per Cu site. In oxygen-free xerogels, Cl K-edge EXAFS revealed the presence of CuI sites with short Cl-Cu bond lengths (RCl−Cu = 2.…