A nanoporous metal–organic framework as a renewable size-selective hydrogen-bonding catalyst in water

Abstract

A novel squaramide-containing metal-organic framework (MOF) material has been designed and synthesized. A detailed X-ray crystal structure analysis showed that four squaramides of this MOF adopted two orientations in each dependent nanopore, confirming that two carbonyl and two N-H groups pointed simultaneously to the inside of the one-dimensional nanometer channel. The MOF was applied as an efficient bifunctional hydrogen-bonding catalyst for Michael additions of 1,3-dicarbonyl compounds to nitroalkenes in pure water, boosting the catalytic efficiency by up to approximately five times the value afforded by the homogeneous control and exhibiting a highly size-selective catalytic performance and good renewability. The catalytic mechanism was also discussed in detail. The present study provides a highly promising approach to achieving dual-activation catalytic centers in a single system, which function as microscopic chemical reactors that allow the interaction and fast transport of substrate molecules in their cavities.