Hybrid Perovskites, Metal–Organic Frameworks, and Beyond: Unconventional Degrees of Freedom in Molecular Frameworks

[Image: see text] The structural degrees of freedom of a solid material are the various distortions most straightforwardly activated by external stimuli such as temperature, pressure, or adsorption. One of the most successful design strategies in materials chemistry involves controlling these individual distortions to produce useful collective functional responses. In a ferroelectric such as lead titanate, for example, the key degree of freedom involves asymmetric displacements of Pb(2+) and Ti(4+) cations; it is by coupling these together that the system as a whole interacts with external electric fields. Collective rotations of the polyhedral units in oxide ceramics are another commonly exploited distortion, driving anomalous behavior such as negative thermal expansion—the counterintuitive phenomenon of volume contraction on heating. An exciting development in the field has been to take advantage of the interplay between different distortion types: generating polarization by combining two different polyhedral rotations, for example. In this way, degrees of freedom act as geometric “elements” that can themselves be combined to engineer materials with new and interesting properties. Just as the discovery of new chemical elements quite obviously diversified chemical space, we might expect that identifying new and different types of structural degrees of freedom to be an important strategy for developing new kinds of functional materials. In this context, the broad family of molecular frameworks is emerging as an extraordinarily fertile source of new and unanticipated distortion types, the vast majority of which have no parallel in the established families of conventional solid-state chemistry. Framework materials are solids whose structures are assembled from two fundamental components: nodes and linkers. Quite simply, linkers join the nodes together to form scaffolding-like networks that extend from the atomic to the macroscopic scale. These structures usually contain cavities, which can also accommodate additional ions for charge balance. In the well-established systems—such as lead titanate—node, linker, and extra-framework ions are all individual atoms (Ti, O, and Pb, respectively). But in molecular frameworks, at least one of these components is a molecule. In this Account, we survey the unconventional degrees of freedom introduced through the simple act of replacing atoms by molecules. Our motivation is to understand the role these new distortions play (or might be expected to play) in different materials properties. The various degrees of freedom themselves—unconventional rotational, translational, orientational, and conformational states—are summarized and described in the context of relevant experimental examples. The much-improved prospect for generating emergent functionalities by combining these new distortion types is then discussed. We highlight a number of directions for future research—including the design and application of hierarchically structured phases of matter intermediate to solids and liquid crystals—which serve to highlight the extraordinary possibilities for this nascent field.