Through millions of years of evolution, nature has used confinement and compartmentalization to access otherwise slow or forbidden pathways and achieve high selectivity under mild conditions. This has inspired scientists all over the world to study the effects of reactant confinement in non-conventional media on their chemical properties and reactivity. The fields of photochemistry and photocatalysis, among others, have also capitalized on the benefits of spatial confinement, which are related to changes in key properties such as light absorption, formation of redox intermediates, lifetime of excited species, thermodynamics of reacting mixtures, kinetics of competitive steps and adsorption/desorption of chemical species. Within this context, the use of supramolecular gels as confined microenvironments for photophysical and photochemical processes has been recognized as an emerging research area. This field is presented by means of case studies and the respective benefits provided by the gel medium. Specifically, examples involving photo-initiated oxidation of alcohols, reduction of aryl halides, chemoselective C-H arylation and trifluoromethylation reactions are presented. These preliminary results open the door for future work involving bond activation pathways that are inaccessible in solution under very mild conditions.

Gel networks as confined microenvironments for photochemical reactions under mild conditions

254th National Meeting (2017)

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