Electronic Effects of Linker Substitution on Lewis Acid Catalysis with Metal–Organic Frameworks

Functionalized linkers can greatly increase the activity of metal-organic framework (MOF) catalysts with coordinatively unsaturated sites. A clear linear free-energy relationship (LFER) was found between Hammett σ(m) values of the linker substituents X and the rate k(X) of a carbonyl-ene reaction. This is the first LFER ever observed for MOF catalysts. A 56-fold increase in rate was found when the substituent is a nitro group.