Abstract
Changing the perception of defects as imperfections in crystalline frameworks into correlated domains amenable to chemical control and targeted design might offer opportunities for the design of porous materials with superior performance or distinctive behavior in catalysis, separation, storage, or guest recognition. From a chemical standpoint, the establishment of synthetic protocols adapted to control the generation and growth of correlated disorder is crucial to consider defect engineering a practicable route towards adjusting framework function. By using UiO-66 as experimental platform, we systematically explored the framework chemical space of the corresponding defective materials. Periodic disorder arising from controlled generation and growth of missing cluster vacancies can be chemically controlled by the relative concentration of linker and modulator, which has been used to isolate a crystallographically pure "disordered" reo phase. Cs-corrected scanning transmission electron microscopy is used to proof the coexistence of correlated domains of missing linker and cluster vacancies, whose relative sizes are fixed by the linker concentration. The relative distribution of correlated disorder in the porosity and catalytic activity of the material reveals that, contrarily to the common belief, surpassing a certain defect concentration threshold can have a detrimental effect.