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 (1C/C, 1Si/C and 1Si/Si) are studied. Three distinct phases for 1C/C and four for 1Si/C and 1Si/Si are fully structurally characterized. The transitions between these phases involve extreme yet recoverable molecular‐level framework reorganization. It is demonstrated that these transformations are related to water content and can be controlled by humidity, and that the non‐porous anhydrous phase of 1C/C shows reversible water sorption through single crystal to crystal restructuring. This mechanistic insight opens the way for the future use of the inherent dynamism present in hydrogen bonded frameworks.

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...

Mixed donor phenanthroline-carboxylate linkers were combined with MnII or ZnII to form photoactive MOFs with large pore apertures. The MOFs display high CO2 adsorption capacities, which consequently causes structural framework...

Reactive extrusion printing (REP) is demonstrated as an approach to simultaneously crystallize and deposit films of the metal–organic framework (MOF) Cu3btc2 (btc=1,3,5‐benzenetricarboxylate), also known as HKUST‐1. The technique co‐delivers inks of the copper(II) acetate and H3btc 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 Cu3btc2 films are produced in low‐dispersity interconnected nanoparticulate form. The porosity was examined using gas adsorption which showed REP gives Cu3btc2 films with open interconnected pore structures, demonstrating the method bestows features that traditional synthesis does not. REP is a technique that opens the field to time‐efficient large‐scale fabrication of MOF interfaces and should find use in a wide variety of coating application settings.

The solvothermal reaction of 2-nitro-[1,1′‐biphenyl]‐4,4′‐dicarboxylic acid (H2bpdcNO2) with Zn(NO3)2·6H2O in DMF solvent does not give a functionalised variant of IRMOF-9. Single-crystal X-ray diffraction analysis shows the major initial product of this reaction, WUF-21 (WUF=Wollongong University Framework), is a porous interpenetrated diamondoid metal–organic framework (MOF) with a secondary building unit that ‘doubly straps’ eight bridging bpdcNO2 ligands in a distorted tetrahedral shape around an unusual pentazinc core. A second porous MOF phase (WUF-23) containing a large and novel dodecazinc secondary building unit forms in the same reaction and eventually predominates in solutions containing formate anion, which arises from the hydrolysis of DMF. Doping the starting ligand with [1,1′‐biphenyl]‐4,4′‐dicarboxylic acid (H2bpdc) provides a facile way to grow nitro-functionalised IRMOF-9, hereafter denoted as WUF-22, where the dopant is carried through into the product. Activated WUF-22 is a microporous solid with an apparent Brunauer–Emmett–Teller (BET) surface area of 2497m2g−1, which matches well with geometric surface area calculations. The CO2 adsorption properties of WUF-22 are reported.