Post-synthetic modification of zirconium metal–organic frameworks by catalyst-free aza-Michael additions

Abstract

UiO-66-NH2 reacts with acrylonitrile, acrylic acid, methyl acrylate and methyl vinyl ketone leading to post-synthetic modification of the MOF through C–N bond formation. The acrylonitrile-modified MOF undergoes further reaction to form a tetrazolate-modified MOF.

Strategies for Pore Engineering in Zirconium Metal-Organic Frameworks

“…For example, one of the most widely studied post-synthetic reactions in Zr-MOFs is covalent modifications at the pendant amino units with various substrates including aziridines, acid anhydrides, and aldehydes in functionalized Zr-MOFs. [136][137][138] Another way to efficiently engineer a pore environment with controllable loadings of functional groups is through click reactions, such as copper-catalyzed azide-alkyne cycloaddition (CuAAC) and inverse-electron demand Diels-Alder (iEDDA) reactions (Figure 9B). [139][140][141][142] Quantitative CuAAC reactions can be utilized to place varying functional groups with controlled loading and density in MOFs through the reaction of azide groups and alkynes, while iEDDA reactions, widely applied in bioconjugate chemistry, allow for a mild and fast pore modification in MOFs through the reaction between tetrazine groups and alkenyl-based compounds.…”

Room-Temperature Hydrogen Adsorption via Spillover in Pt Nanoparticle-Decorated UiO-66 Nanoparticles: Implications for Hydrogen Storage

“…The UiO-66-NH 2 has the formula Zr 6 O 4 (OH) 4 (BDC-NH 2 ) 6 with a molecular weight of 1760.1 g/mol. 67 Considering that there are 12 COO in one UiO-66 unit, there will be 12 H addition if all carboxylate groups are hydrogenated. The numbers lead to about 0.68 wt % hydrogen adsorption, which basically agrees with our maximum observation.…”

Inclusion and release of ant alarm pheromones from metal–organic frameworks

“…UiO-66 and its analogues are stable in acids, so cannot be digested in the same way as IRMOFs. Instead, samples were digested using aqueous ammonium fluoride solution, 28 and analysed, following digestion, by 1 H NMR spectroscopy. The analysis revealed that the sample had included 35.1 wt% 3-octanone so UiO-66-NHPr exhibits a lower capacity than IRMOF-NHPr using neat 3-octanone.…”