Tunable synthesis of heteroleptic zirconium-based porous coordination cages

Zirconium-based porous coordination cages have been widely studied and have shown to be potentially useful for many applications as a result of their tunability and stability, likely as a result of their status as a molecular equivalent to the small 8 Å tetrahedral pores of UiO-66 (Zr₆(μ₃-O)₄(μ₂-OH)₄(C₈O₄H₄)₆). Functional groups attached to these molecular materials endow them with a range of tunable properties. While so-called multivariate MOFs containing multiple types of functional groups on different bridging ligands within a structure are common, incorporating multiple functional moieties in permanently microporous molecular materials has proved challenging. By applying a mixed-ligand, or heteroleptic, synthesis strategy to cage formation, we have designed a straight-forward, one-pot synthesis of 10 Å zirconium-based molecular cages in a basket-shaped, or Zr₁₂L₆, geometry containing 3 : 3 ratios of combinations of two types of functional moieties from 11 different ligand options. Additionally, using more sterically hindered ligands, such as 5-benzyloxybenzene dicarboxylate, we show that ligand size governs the resulting cage geometry. This method allows for multiple functional groups to be incorporated in molecular cages and the ratio of moieties incorporated can be easily controlled. With this strategy in hand, we show that ligands for which zirconium cage syntheses have been elusive, such as 2,5-dihydroxybenzene dicarboxylate, have now been successfully incorporated into porous structures.