Hybrid materials are increasingly used for supporting homogeneous catalysts. This review describes the various methodologies used to synthesize such hybrid materials or to graft catalysts on inorganic or hybrid supports. Applications of these materials for reactions mediated by supported organometallic or organic catalysts are presented.

A simple β-diamide ligand was immobilized by the sol–gel process on hybrid silica for Cu-mediated O-arylation reactions. Combined with 5% of CuI, the latter can easily be recovered and reused to generate diarylethers under smooth conditions from cheap aryl bromides in an eco-friendly solvent (MIBK). Besides, negligible metal leaching occurred after reaction in solution from the supported catalyst.

An organic molecule, (EtO)₃Si(CH₂)₃NH(CO)NH–(CH₂)₁₂–NH(CO)NH(CH₂)₃Si(OEt)₃, combining urea functionalities and a 12-carbon alkyl chain, underwent sol–gel reactions in the presence of an acid catalyst, a large excess of water and variable amounts of EuCl₃, giving rise to the formation of crystalline hybrids through a self-directed organization process in which hydrogen bonding interactions play a key role. Three photoluminescent lamellar Eu³⁺-doped silsesquioxane hybrids incorporating 1.01, 1.83 and 15.04% Eu³⁺ were prepared and fully characterized. The lamellar hybrids are room temperature multi-wavelength emitters due to the convolution of the hybrid's emitting centres and the Eu³⁺ intra-4f⁶ transitions. Their emission colour can be easily tuned along the Commission Internationale d'Eclairage chromaticity diagram from the bluish-purple region to the pink area, either by changing the excitation wavelength or the Eu³⁺ amount. The Eu³⁺ first coordination shell is very similar for the three photoluminescent lamellar Eu³⁺-doped silsesquioxane hybrids incorporating oxygen atoms of the carbonyl group, Cl atoms and water molecules, despite the minor variations found in the ⁵D₀ quantum efficiency (16.3–19.2), number of water molecules (1.7–2.0) and experimental intensity Ω₂ parameter (8.9–10.1 × 10⁻²⁰ cm²) with the increase of Eu³⁺ content.