Organophosphorus acids and their derivatives (salts, esters) are quite complementary of organosilicon coupling molecules for the preparation of hybrid organic–inorganic materials, by sol–gel processing or surface modification. Organosilicon compounds are best suited for the anchoring of organic groups to silicon-containing inorganic matrices or supports, such as silica, silicates, silicon carbide, etc., whereas organophosphorus coupling molecules appear well adapted to matrices or supports based on metals or transition metals: oxides, hydroxides, as well as carbonates and phosphates. The different reactivity of organophosphorus coupling molecules leads to different structures and stabilities of the final hybrid materials and may provide decisive advantages in the sol–gel synthesis of homogeneous hybrids, the preparation of surface monolayers or the selective surface modification of nanopatterned supports.

Phosphonic acids are increasingly being used for controlling surface and interface properties in hybrid or composite materials, (opto)electronic devices and in the synthesis of nanomaterials. In this perspective article, a concise survey of phosphonate coupling molecules is first presented, including details on their coordination chemistry, their use in the surface modification of inorganic substrates with self-assembled monolayers, and the analytical techniques available to characterize their environment in nanomaterials. Then, some of their recent applications in the development of organic electronic devices, photovoltaic cells, biomaterials, biosensors, supported catalysts and sorbents, corrosion inhibitors, and nanostructured composite materials, are presented. In the last part of the article, a brief overview of recent progress in the use of phosphonate ligands for the preparation of molecular nanomaterials like metal organic frameworks and functionalized polyoxometalates is given.

Oxides and mixed oxides have a tremendous importance in the field of heterogeneous catalysis, serving either as catalysts or as supports for active species. The performance of a catalyst depends directly on its composition, texture, structure and surface properties, which have to be precisely controlled and adapted to each application. In this context, the sol–gel process is a unique tool for the preparation and understanding of catalytic materials, owing to its exceptional versatility. In the last 10 years, the non-hydrolytic sol–gel (NHSG) or non-aqueous sol–gel process based on nonhydrolytic condensations in nonaqueous media has established itself as a simple and powerful method for the design of a wide range of oxide, mixed oxide and hybrid materials with controlled composition, morphology, texture and structure. NHSG proved particularly interesting for the preparation of catalytic materials, notably mesoporous xerogels, single site catalysts and highly crystalline nanoparticles. This critical review addresses the application of NHSG to the preparation of heterogeneous catalysts, emphasizing the specificities of this process, and giving a comprehensive overview of the literature (251 references).