0000000000583218
AUTHOR
Clément Suspène
Exceptional affinity of nanostructured organic-inorganic hybrid materials towards dioxygen: confinement effect of copper complexes
We report the exceptional reactivity towards dioxygen of a nanostructured organic-inorganic hybrid material due to the confinement of copper cyclam within a silica matrix. The key step is the metalation reaction of the ligand, which can occur before or after xerogel formation through the sol-gel process. The incorporation of a Cu(II) center into the material after xerogel formation leads to a bridged Cu(I)/Cu(II) mixed-valence dinuclear species. This complex exhibits a very high affinity towards dioxygen, attributable to auto-organization of the active species in the solid. The remarkable properties of these copper complexes in the silica matrix demonstrate a high cooperative effect for O(2…
Reversible coordination of dioxygen by tripodal tetraamine copper complexes incorporated in a porous silica framework.
The present study reports the synthesis and rational design of porous structured materials by using a templating method. A tetraethoxysilylated tripodal tetraamine (TREN) was covalently incorporated in a silica framework with a double imprint: A surfactant template and a metal ion imprint. The presence of a cationic surfactant (CTAB) endowed the material with a high porosity, and the tripodal or square-pyramidal topology of the ligand was preserved thanks to the use of the silylated Cu(II) complex. After removal of the surfactant and de-metalation, the incorporated tetraamine was quantitatively complexed by CuCl(2) and the material has shown after thermal activation that a reversible bindin…