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Abstract We report a novel Nb(V)−carboxylate cluster obtained from reaction of niobium(V) ethoxide and pivalic (trimethylacetic) acid. Single crystal X‐ray diffraction data reveal a structure composed of 16 Nb(V) ions featuring oxo‐, ethoxy‐ and pivalate moieties. The new cluster exhibits the highest nuclearity among structurally characterized niobium carboxylates reported to date.
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Abstract Dianionic hyponitrite (N2O22−) is often proposed, based on model complexes, as the key intermediate in reductive coupling of nitric oxide to nitrous oxide at the bimetallic active sites of heme‐copper oxidases and nitric oxide reductases. In this work, we examine the gas‐solid reaction of nitric oxide with the metal–organic framework CuI‐ZrTpmC* with a suite of in situ spectroscopies and density functional theory simulations, and identify an unusual chelating N2O2.−intermediate. These results highlight the advantage provided by site‐isolation in metal–organic frameworks (MOFs) for studying important reaction intermediates, and provide a mechanistic scenario compatible with the proposed one‐electron couple in these enzymes.more » « less
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null (Ed.)Metal–organic frameworks (MOFs) represent one of the most diverse structural classes among solid state materials, yet few of them exhibit aperiodicity, or the existence of long-range order in the absence of translational symmetry. From this apparent conflict, a paradox has emerged: even though aperiodicity frequently arises in materials that contain the same bonding motifs as MOFs, aperiodic structures and MOFs appear to be nearly disjoint classes. In this perspective, we highlight a subset of the known aperiodic coordination polymers, including both incommensurate and quasicrystalline structures. We further comment upon possible reasons for the absence of such structures and propose routes to potentially access aperiodic MOFs.more » « less
