Applying a nanoparticle@mof interface to activate an unconventional regioselectivity of an inert reaction at ambient conditions

• Main Authors: Lee, Hiang Kwee, Koh, Charlynn Sher, Lo, Wei-Shang, Liu, Yejing, Phang, In Yee, Sim, Howard Yi, Lee, Yih Hong, Phan-Quang, Gia Chuong, Tsung, Chia-Kuang, Ling, Xing Yi
• Other Authors: School of Physical and Mathematical Sciences
• Format: Article
• Language: English
• Published: 2021
• Subjects: Science::Chemistry; Interfaces; Organic Reactions
• Online Access: https://hdl.handle.net/10356/151910
• Institution: Nanyang Technological University

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.