Reticular Chemistry in Its Chiral Form: Axially Chiral Zr(IV)-Spiro Metal–Organic Framework as a Case Study

The interplay of primary organic ligands and inorganic secondary building units (SBUs) has led to a continual boom of reticular chemistry, particularly metal–organic frameworks (MOFs). Subtle variations of organic ligands can have a significant impact on the ultimate structural topology and consequently, the material's function. However, the role of ligand chirality in reticular chemistry has rarely been explored. In this work, we report the organic ligand chirality-controlled synthesis of two zirconium-based MOFs (Spiro-1 and Spiro-3) with distinct topological structures as well as a temperature-controlled formation of a kinetically stable phase (Spiro-4) based on the carboxylate-functionalized inherently axially chiral 1,1′-spirobiindane-7,7′-phosphoric acid ligand. Specifically, Spiro-1 is a homochiral framework comprising only enantiopure S-spiro ligands and has a unique 4,8-connected sjt topology with large 3D interconnected cavities, while Spiro-3 contains equal amounts of S- and R-spiro ligands, resulting in a racemic framework of 6,12-connected edge-transitive alb topology with narrow channels. Interestingly, the kinetic product Spiro-4 obtained with racemic spiro ligands is built of both hexa- and nona-nuclear zirconium clusters acting as 9- and 6-connected nodes, respectively, giving rise to a newly discovered azs net. Notably, the preinstalled highly hydrophilic phosphoric acid groups combined with large cavity, high porosity, and outstanding chemical stability endow Spiro-1 with remarkable water vapor sorption performance, whereas Spiro-3 and Spiro-4 show poor performances due to inappropriate pore systems and structural fragility upon the water adsorption/desorption process. This work highlights the important role of ligand chirality in manipulating the framework topology and function and would further enrich the development of reticular chemistry.