Modulator Effect in UiO-66-NDC (1,4-Naphthalenedicarboxylic Acid) Synthesis and Comparison with UiO-67-NDC Isoreticular Metal–Organic Frameworks

A zirconium metal–organic framework with UiO-66 topology was synthesized using a 1,4-naphthalenedicarboxylic acid (NDC) linker (UiO-66-NDC). From synchrotron powder X-ray diffraction (PXRD), we found that the naphthalene rings of the NDC linker are out of (a,c)-plane equilibrium by 30°, similar to the situation found by single crystal XRD for the benzene rings in UiO-67 (Cryst. Growth Des. 2014, 14, 5370). Different fractions of the benzene-carboxylic (BC) acid modulator versus NDC were used to tune structural properties of the final product. The modulator increases both the crystal size and the surface area of the product, but reduces its thermal stability owing to insertion of defects: missing linkers and missing Zr6(OH)4O4 clusters. This study proves that the defect density (fraction of BC incorporation) can be tuned in UiO-66-NDC materials up to almost 50%. At that stage, the crystal is characterized also by a high density of missing Zr6(OH)4O4 inorganic cornerstones. Notwithstanding such structural d...