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

Timothy A. Ablott, Rhian Webby, Daniel R. Jenkinson, Alexandra Nikolich, Lujia Liu, Harina Amer Hamzah, Mary F. Mahon, Andrew D. Burrows, Christopher Richardson

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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.

Original languageEnglish
Pages (from-to)1136-1144
Number of pages9
JournalInorganic Chemistry
Issue number2
Early online date3 Jan 2022
Publication statusPublished - 17 Jan 2022

Bibliographical note

Funding Information:
T.A.A. acknowledges the Australian Government for an Australian Government Research Training Program Award. C.R. thanks the University of Wollongong for financial support.

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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