A simple and non-destructive method for assessing the incorporation of bipyridine dicarboxylates as linkers within metal-organic frameworks

As a novel avenue for applications, metal-organic frameworks (MOFs) are increasingly used for heterogenizing catalytic molecular species as linkers into their crystalline framework. These multifunctional compounds can be accessed with mixed linkers synthesis or postsynthetic-exchange strategies. Major limitations still reside in their challenging characterization; in particular, to provide evidence of the genuine incorporation of the functionalized linkers into the framework and their quantification. Herein, we demonstrate that a combination of computational chemistry, spectroscopy and X-ray diffraction allows access to a non-destructive analysis of mixed-linker UiO-67-type materials featuring biphenyl- and bipyridine-dicarboxylates. Our UV/Vis-based methodology has been further applied to characterize a series of Rh-functionalized UiO-67-type catalysts. The proposed approach allows a recurrent key issue in the characterization of similar supported organometallic systems to be solved.