Among the numerous fascinating properties of metal–organic frameworks (MOFs), their rotational dynamics is perhaps one of the most intriguing, with clear consequences for adsorption and separation of molecules, as well as for optical and mechanical properties. A closer look at the rotational mobility in MOF linkers reveals that it is not only a considerably widespread phenomenon, but also a fairly diverse one. Still, the impact of these dynamics is often understated. In this review, we address the various mechanisms of linker rotation reported in the growing collection of literature, followed by a highlight of the methods currently used in their study, and we conclude with the impacts that such dynamics have on existing and future applications.

The inclusion of Ti(IV) in water-stable metal-organic frameworks has been proposed as a strategy for the generation of high surface area heterogeneous photocatalysts, with UiO-66 being a promising candidate. We find that the site of binding of Ti(IV) is at linker defect sites and not incorporated into the inorganic secondary building unit through metal exchange. We also demonstrate the choice of titanium source is critical in the generation of an active hydrogen evolution catalyst, and explain the observed activity using density functional theory calculations, which also enable rational design of future Ti(IV) coordination environments in MOF catalysts.

The organic components in metal−organic frameworks (MOFs) are unique: they are embedded in a crystalline lattice, yet, as they are separated from each other by tunable free space, a large variety of dynamic behavior can emerge. These rotational dynamics of the organic linkers are especially important due to their influence over properties such as gas adsorption and kinetics of guest release. To fully exploit linker rotation, such as in the form of molecular machines, it is necessary to engineer correlated linker dynamics to achieve their cooperative functional motion. Here, we show that for MIL-53, a topology with closely spaced rotors, the phenylene functionalization allows researchers to tune the rotors' steric environment, shifting linker rotation from completely static to rapid motions at frequencies above 100 MHz. For steric interactions that start to inhibit independent rotor motion, we identify for the first time the emergence of coupled rotation modes in linker dynamics. These findings pave the way for function-specific engineering of gear-like cooperative motion in MOFs.