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We report two porous Zr phosphonate frameworks. The kinetic product, ZrH2L-A, shows low order and is less porous. An HF-modulated structure, CALF-31, is more ordered and has higher porosity. While not single crystalline, CALF-31 is highly robust and the CO2 heats of adsorption give insights into ordering in phosphonate MOFs.

Graphical abstract: Reconciling order, stability, and porosity in phosphonate metal–organic frameworks via HF-mediated synthesis

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