Reactive Extrusion Printing of Zeolitic Imidazolate Framework Films.

An outstanding challenge for the field of metal-organic frameworks (MOFs) is structuring to form forms with greater useability. Reactive extrusion printing (REP) is a technique for the direct formation of films from their molecular components on-demand and on-location. Here we apply REP for the first time to zeolitic imidazolate frameworks (ZIFs) and study the interplay of solvent and molarity ratio on the phase distribution between ZIF-8 and ZIF-L in reactive printed films.

Water Sorption Controls Extreme Single-Crystal-to-Single-Crystal Molecular Reorganization in Hydrogen Bonded Organic Frameworks.

As hydrogen bonded frameworks are held together by relatively weak interactions, they often form several different frameworks under slightly different synthesis conditions and respond dynamically to stimuli such as heat and vacuum. However, these dynamic restructuring processes are often poorly understood. In this work, three isoreticular hydrogen bonded organic frameworks assembled through charge-assisted amidinium⋅⋅⋅carboxylate hydrogen bonds (1 , 1 and 1 ) are studied.

Reactive Extrusion Printing for Simultaneous Crystallization-Deposition of Metal-Organic Framework Films.

Reactive extrusion printing (REP) is demonstrated as an approach to simultaneously crystallize and deposit films of the metal-organic framework (MOF) Cu btc (btc=1,3,5-benzenetricarboxylate), also known as HKUST-1. The technique co-delivers inks of the copper(II) acetate and H btc starting materials directly on-surface and on-location for rapid nucleation into films at room temperature. The films were analyzed using PXRD, profilometry, SEM and thermal analysis techniques and confirmed high-quality Cu btc films are produced in low-dispersity interconnected nanoparticulate form.

Rapid spatially-resolved post-synthetic patterning of metal-organic framework films.

Reactive inkjet printing was used for fast and facile spatially-controlled post-synthetic patterning of metal-organic framework films. Here, we report use of the reactive inkjet printing technique to rapidly produce patterned electroactive MOF films by covalent attachment of redox-responsive ferrocenyl groups to UiO-66-NH2 on FTO glass. This study paves the way for the wide applicability of reactive printing to MOF film modification.

Mixed donor, phenanthroline photoactive MOFs with favourable CO selectivity.

Mixed donor phenanthroline-carboxylate linkers were combined with Mn or Zn to form photoactive MOFs with large pore apertures. The MOFs display high CO adsorption capacities, which consequently causes structural framework flexibility, and align with favorable metrics for selective CO capture. The photophysical properties of the MOFs were investigated, with the Mn MOF giving rise to short triplet LMCT lifetimes.