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Novel two-dimensional kagome metal-organic frameworks with mononuclear Zr4+/Hf4+ nodes chelated by benzene-1,4-dihydroxamate linkers were synthesized. The MOFs, namely SUM-1, are chemically robust and kinetically favorable, as confirmed by theoretical and...

Inspired by hydroxamate-based siderophores, here we report the synthesis of a novel two-dimensional (2D) Fe-hydroxamate metal-organic framework (MOF), namely SUM-31. The MOF, constructed from homoleptic Fe(hydroxamate)3 nodes and linear E-ethylenedihydroxamate...

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Synthetic efforts targeting highly symmetrical metal–organic frameworks (MOFs) have always been relentless, for the symmetry of a MOF’s pore environment and overall crystal structure are relevant to the MOF’s properties and behavior. Herein, we report a novel Th-based MOF constructed from assembling highly symmetrical Th-oxo clusters via in situ reductive coupling of nitroso groups on the cluster surface. Nitroso groups have long been known to dimerize in a reversible fashion. Putting them on the monovalent ligands that decorate the Th-oxo clusters can facilitate a downstream assembly process that link the said clusters in a controllable and predictable manner, preserving the overall symmetry in the MOF product. Moreover, the assembly can be made permanent by reducing the azodioxy moiety to azo, effectively locking the symmetrical MOF form. We believe this process of assembling pre-formed Th-oxo clusters helps the overall MOF adopt a highly symmetrical topology (face-centered cubic, fcu) resembling the well-known UiO series MOFs based on tetravalent Zr/Hf.