SOMC@PMS. Surface organometallic chemistry at periodic mesoporous silica

Periodic mesoporous silicas (PMSs) give enormous stimulus to the field of nanostructured organic-inorganic composite materials, opening new horizons for selective organic transformations and material science. This article outlines advanced synthetic concepts of their intraporous surface organometallic chemistry involving alkyl, (silyl)amide, and alkoxide reagents. Conclusive methods of characterization, elaborating the importance of spectroscopic probe ligands and nitrogen physisorption, reinforce the excellent capacity of PMS materials as a model support of, for example, amorphous silica. Particular emphasis is placed on tailor-made hybrid materials, highlighting unexpected reaction behavior due to surface and pore confinement. Accordingly, surface silylation as an efficient method for designing the microenvironment is surveyed in detail.