Applying a Nanoparticle@MOF Interface To Activate an Unconventional Regioselectivity of an Inert Reaction at Ambient Conditions.

Here we design an interface between a metal nanoparticle (NP) and a metal-organic framework (MOF) to activate an inert CO2 carboxylation reaction and in situ monitor its unconventional regioselectivity at the molecular level. Using a Kolbe-Schmitt reaction as model, our strategy exploits the NP@MOF interface to create a pseudo high-pressure CO2 microenvironment over the phenolic substrate to drive its direct C-H carboxylation at ambient conditions. Conversely, Kolbe-Schmitt reactions usually demand high reaction temperature (>125 °C) and pressure (>80 atm). Notably, we observe an unprecedented CO2 meta-carboxylation of an arene that was previously deemed impossible in traditional Kolbe-Schmitt reactions. While the phenolic substrate in this study is fixed at the NP@MOF interface to facilitate spectroscopic investigations, free reactants could be activated the same way by the local pressurized CO2 microenvironment. These valuable insights create enormous opportunities in diverse applications including synthetic chemistry, gas valorization, and greenhouse gas remediation.