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

Herein, we report coupling in situ 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 (H₂bpdcOCH₂CCH) 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 Me₂bpdcOCH₂CCH and proceeded far more easily than the solid-state transformation from H₂bpdcOCH₂CCH, showing the potential of MOFs to give rise to different chemistry. The major oxidative process was thermolysis of the chromene ring with a minor pathway of allylic-type oxidation to give heterocyclic chromenone functionality. The sequence was also successful on a series of two-component multivariate IRMOF frameworks prepared from thermo-reactive H₂bpdcOCH₂CCH and thermo-resistant H₂bpdcOMe linkers, demonstrating that these reactions can be used with known crystal engineering strategies. All transformations were fully compatible with the requirements to maintain MOF crystallinity and porosity as evidenced by surface area analysis and X-ray powder diffraction measurements. This work contributes to establishing the feasibility of high-temperature solid–gas manifolds for MOF PSM.