Several metal–organic frameworks (MOFs) excel in harvesting water from the air or as heat pumps as they show a steep increase in water uptake at 10–30 % relative humidity (RH%). A precise understanding of which structural characteristics govern such behavior is lacking. Herein, CAU-10-H and CAU-10-CH₃ are studied with -H, -CH₃ corresponding to the functions grafted to the organic linker. CAU-10-H shows a steep water uptake ≈18 RH% of interest for water harvesting, yet the subtle replacement of -H by -CH₃ in the organic linker drastically changes the water adsorption behavior to less steep water uptake at much higher humidity values. The materials’ structural deformation and water ordering during adsorption with in situ sum-frequency generation, in situ X-ray diffraction, and molecular simulations are unraveled. In CAU-10-H, an energetically favorable water cluster is formed in the hydrophobic pore, tethered via H-bonds to the framework μ-OH groups, while for CAU-10-CH₃, such a favorable cluster cannot form. By relating the findings to the features of water adsorption isotherms of a series of MOFs, it is concluded that favorable water adsorption occurs when sites of intermediate hydrophilicity are present in a hydrophobic structure, and the formation of energetically favorable water clusters is possible.

A modulated synthesis approach based on the chelating properties of oxalic acid (H₂C₂O₄) is presented as a robust and versatile method to achieve highly crystalline Al-based metal-organic frameworks. A comparative study on this method and the already established modulation by hydrofluoric acid was conducted using MIL-53 as test system. The superior performance of oxalic acid modulation in terms of crystallinity and absence of undesired impurities is explained by assessing the coordination modes of the two modulators and the structural features of the product. The validity of our approach was confirmed for a diverse set of Al-MOFs, namely X-MIL-53 (X=OH, CH₃O, Br, NO₂), CAU-10, MIL-69, and Al(OH)ndc (ndc=1,4-naphtalenedicarboxylate), highlighting the potential benefits of extending the use of this modulator to other coordination materials.

Every measurement technique operates on a given timescale and measurements using emissive small molecule sensors are no exception. A family of luminescent sensors providing first optical characterization of dynamic phenomena in polymers at a timescale of several microseconds is described. This performance originates from the dynamics manifested in the excited state of the sensor molecules where diffusioncontrolled events select the emission color while radiative phenomena define the global operation timescale. Since the mechanism responsible for signal generation is confined to the short lived excited state of emissive probe, it is possible observe an unprecedented link between the timescale of sensory action and that of photoluminescence. An application of this new methodology is demonstrated by performing general, short timescale detection of glass transitions in a temperature ranges precluding the informative range of conventional techniques by tens of degrees.

The coordination chemistry of Metal-Organic Frameworks is one key aspect when their applications and performances enhancement are pursued. This is usually investigated while cation exchanges or functionalisation reactions on open metal sites are involved. In this work we present a rare case of solvent coordination-induced breathing behaviour of a renowned Zn-based MOF, namely IRMOF-9, whose structural flexibility allows its framework topology to be retained upon dramatic coordination changes on their inorganic nodes. These are observed to accept from one to three additional coordination bonds from solvent molecules, depending on the coordination power of these latter and on temperature conditions. Structural studies by Single Crystal X-Ray Diffraction afforded precious insights on the occurring of such coordinative changes, suggesting that solvent molecules which dynamically bind the metal atoms are capable to play a decisive role in the final geometry of the framework.