Coupling Postsynthetic High-Temperature Oxidative Thermolysis and Thermal Rearrangements in Isoreticular Zinc MOFs.

Herein, we report coupling high temperature postsynthetic modifications (PSMs) in metal-organic frameworks (MOFs). Thermo-reactive propargyloxy-functionalized zinc IRMOFs (isoreticular metal-organic frameworks) prepared from 2-(prop-2-yn-1-yloxy)-[1,1'-biphenyl]-4,4'-dicarboxylic acid (HbpdcOCHCCH) were investigated for their high-temperature postsynthetic rearrangement (PSR) chemistry to heterocyclic chromenes and benzofurans and then coupled to solid-gas reactions with molecular oxygen. The selectivity for the initial molecular rearrangements was found to be inverted in the porous MOF environment compared to conventional melt reactions of the ester compound MebpdcOCHCCH and proceeded far more easily than the solid-state transformation from HbpdcOCHCCH, showing the potential of MOFs to give rise to different chemistry.