Facile and Rapid Room-Temperature Electrosynthesis and Controlled Surface Growth of Fe-MIL-101 and Fe-MIL-101-NH.

The electrochemical synthesis of metal-organic frameworks (MOFs) has been widely explored but has involved indirect routes, including anodic dissolution of solid metal electrodes or the use of interfacial redox chemistry to generate base equivalents and drive MOF assembly. These methods are limited in scope, as the former relies on the use of an anode consisting of the metal ion to be incorporated into the MOF, and the latter relies on the compatibility of the metal/ligand solution with the probase that is subsequently oxidized or reduced. We report the facile, direct electrochemical syntheses of four iron-based MOFs via controlled potential oxidation of dissolved metal cations.

On the Way to a Trisanionic {Cu O } Core for Oxidase Catalysis: Evidence of an Asymmetric Trinuclear Precursor Stabilized by Perfluoropinacolate Ligands.

Cu complexes of the form K[(R P)Cu(pin )], in which (pin ) is the bidentate, oxygen-donating ligand perfluoropinacolate, were synthesized and characterized. Low-temperature oxygenation of the K[(R P)Cu(pin )(PR )] species resulted in a trisanionic bis(μ -oxo) trinuclear copper(II,II,III) core characterized by UV/Vis spectroscopy (λ [nm] = 330, 535, 630), cryospray-ionization mass spectrometry, and X-band electron paramagnetic resonance spectroscopy (derivative resonance at 3300 G, Δm =2 at 1500 G). The kinetic behavior of the trimeric {Cu O } species was quantified by stopped-flow spectroscopy and the associated electronic structures were investigated by DFT calculations.