Guest-Controlled Incommensurate Modulation in a Meta-Rigid Metal-Organic Framework Material

Structural transitions of host systems in response to guest binding dominate many chemical processes. We report an unprecedented type of structural flexibility within a meta-rigid material, MFM-520, which exhibits a reversible periodic-to-aperiodic structural transition resulting from a drastic distortion of a [ZnO4N] node controlled by the specific host-guest interactions. The aperiodic crystal structure of MFM-520 has no three-dimensional (3D) lattice periodicity but shows translational symmetry in higher-dimensional (3 + 2)D space. We have directly visualized the aperiodic state which is induced by incommensurate modulation of the periodic framework of MFM-520·H2O upon dehydration to give MFM-520. Filling MFM-520 with CO2 and SO2 reveals that, while CO2 has a minimal structural influence, SO2 can further modulate the structure incommensurately. MFM-520 shows exceptional selectivity for SO2 under flue-gas desulfurization conditions, and the facile release of captured SO2 from MFM-520 enabled the conversion to valuable sulfonamide products. MFM-520 can thus be used as a highly efficient capture and delivery system for SO2

A HF Loaded Lewis-Acidic Aluminium Chlorofluoride for Hydrofluorination Reactions

The very strong Lewis acid aluminium chlorofluoride (ACF) was loaded with anhydrous HF. The interaction between the surface of the catalyst and HF was investigated using a variety of characterization methods, which revealed the formation of polyfluorides. Moreover, the reactivity of the HF-loaded ACF towards the hydrofluorination of alkynes was studied.Peer Reviewe

Drug Guest Molecules as Modulators During One-Step Mechanochemical Encapsulation in MIL-100 (Fe) Framework

We propose a facile one-pot mechanochemical strategy for the encapsulation of drug guest molecules (e.g. 5‑fluorouracil, caffeine, and aspirin) in MIL-100 (Fe) as the porous host framework. We reveal the modulating effect of 5-FU and caffeine, giving highly crystalline MIL‑100 (Fe), whereas aspirin led to the formation of an amorphous MOF phase. Inelastic neutron scattering (INS) was used to probe the intermolecular interactions underpinning the drug@MIL‑100 assemblies, where strong guest-host interaction was achieved via this eco-friendly approach.</p

A HF Loaded Lewis‐Acidic Aluminium Chlorofluoride for Hydrofluorination Reactions

The very strong Lewis acid aluminium chlorofluoride (ACF) was loaded with anhydrous HF. The interaction between the surface of the catalyst and HF was investigated using a variety of characterization methods, which revealed the formation of polyfluorides. Moreover, the reactivity of the HF-loaded ACF towards the hydrofluorination of alkynes was studied.Peer Reviewe

Direct Evidence for Solid-like Hydrogen in a Nanoporous Carbon Hydrogen Storage Material at Supercritical Temperatures

Here we report direct physical evidence that confinement of molecular hydrogen (H2) in an optimized nanoporous carbon results in accumulation of hydrogen with characteristics commensurate with solid H2 at temperatures up to 67 K above the liquid–vapor critical temperature of bulk H2. This extreme densification is attributed to confinement of H2 molecules in the optimally sized micropores, and occurs at pressures as low as 0.02 MPa. The quantities of contained, solid-like H2 increased with pressure and were directly evaluated using in situ inelastic neutron scattering and confirmed by analysis of gas sorption isotherms. The demonstration of the existence of solid-like H2 challenges the existing assumption that supercritical hydrogen confined in nanopores has an upper limit of liquid H2 density. Thus, this insight offers opportunities for the development of more accurate models for the evaluation and design of nanoporous materials for high capacity adsorptive hydrogen storage