The state of the art concerning the use of thiol functionalities for the preparation of porous monolithic structures and modulation of their surface chemistry thus enabling a variety of applications is reviewed. The preparation of monoliths with thiol groups is achieved via a single-pot strategy or a parent monolith is prepared followed by post-synthesis modification.
Both strategies lead to monolithic structures which applications benefit from the reactivity of thiols. Current thiol functionalized monoliths are formed from silica, synthetic polymers, and hybrid organic-silica materials.
Preparation of monolithic columns for chromatography is described as well as the production of heterogeneous catalytic reactors in which the affinity of metal nanoparticles to thiols is used. The application of thiol-ene click reactions for the construction of polymer monoliths is then illustrated.
Finally, we discuss the hybrid organic-silica monoliths emphasizing their preparation from polyhedral oligomeric silsesquioxanes. These monoliths are well suited for functionalizations and assist the various click reactions.