A Study Using X-ray Absorption and Emission Spectroscopy of Dioxygen-Binding Xerogels Incorporating Cyclam Units Complexed with Copper Salts. - Université de Bourgogne Accéder directement au contenu
Article Dans Une Revue European Journal of Inorganic Chemistry Année : 2005

A Study Using X-ray Absorption and Emission Spectroscopy of Dioxygen-Binding Xerogels Incorporating Cyclam Units Complexed with Copper Salts.

Résumé

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 -1:1 peroxo-like conformation with unequal Cu···O distances. Only the short distance (RCu-O1 = 1.86 ± 0.01 Å) was unambiguously determined and looks typical of a CuII site. The Cu···Cu internuclear distances would be rather long: RCu-Cu 4.0 Å (3.9 Å) 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 Å). Pentacoordinate CuII sites with a longer Cl-Cu bond (2.45 ± 0.03 Å) were also identified. Another signal at a further distance (2.73 ± 0.03 Å) suggests that the Cl ions could bridge mixed-valence {CuI,CuII} sites. In oxygenated xerogels complexed with CuCl2, ca. 75 % of the Cu atoms would be singly bound to dioxygen while the signature of the pentacoordinate CuII sites would totally vanish. Substituting CuBr2 for CuCl2 yields xerogels with a poor capability to bind dioxygen. This is remarkably correlatedwith a decrease of the signatures at RCu-O1 = 1.86 Å and RCu-Cu 4.0 Å. EXAFS spectra of the oxygen-free xerogel complexed with CuBr2 again exhibit signatures assigned to short (2.30 Å)/long (2.49 Å) Cu-Br bonds as expected for mixed-valence {CuI,CuII} systems. Inactive xerogels prepared with metallated cyclams seem to undergo a structural change during hydrolysis and polycondensation. Deconvoluted XANES spectra of the active xerogels exhibit a strong pre-edge resonance which is characteristic of mixed-valence CuI sites. This interpretation was supported by ab initio XANES simulations carried out beyond the muffin-tin approximation.

Dates et versions

hal-00020236 , version 1 (08-03-2006)

Identifiants

Citer

José Goulon, Chantal Goulon-Ginet, Andrei Rogalev, Fabrice Wilhelm, Nicolas Jaouen, et al.. A Study Using X-ray Absorption and Emission Spectroscopy of Dioxygen-Binding Xerogels Incorporating Cyclam Units Complexed with Copper Salts.. European Journal of Inorganic Chemistry, 2005, 13, pp.2714-2726. ⟨10.1002/ejic.200401027⟩. ⟨hal-00020236⟩
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