Chemical complexity for targeted function in heterometallic titanium–organic frameworks

Research on metal–organic frameworks is shifting from the principles that control the assembly, structure, and porosity of these reticular solids, already established, into more sophisticated concepts that embrace chemical complexity as a tool for encoding their function or accessing new properties by exploiting the combination of different components (organic and inorganic) into these networks. The possibility of combining multiple linkers into a given network for multivariate solids with tunable properties dictated by the nature and distribution of the organic connectors across the solid has been well demonstrated. However, the combination of different metals remains still comparatively underexplored due to the difficulties in controlling the nucleation of heterometallic metal-oxo clusters during the assembly of the framework or the post-synthetic incorporation of metals with distinct chemistry. This possibility is even more challenging for titanium–organic frameworks due to the additional difficulties intrinsic to controlling the chemistry of titanium in solution. In this perspective article we provide an overview of the synthesis and advanced characterization of mixed-metal frameworks and emphasize the particularities of those based in titanium with particular focus on the use of additional metals to modify their function by controlling their reactivity in the solid state, tailoring their electronic structure and photocatalytic activity, enabling synergistic catalysis, directing the grafting of small molecules or even unlocking the formation of mixed oxides with stoichiometries not accessible to conventional routes.