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.
Bibliographical noteFunding Information:
The computational work was facilitated by access to the UK National Supercomputer, ARCHER (EPSRC Grant EP/L000202) and XSEDE (NSF Grant ACI-1053575). C.M.D. thank the French National Research Agency (ANR project: HOPFAME ANR-13-BS07-0002-01) and acknowledges support from the Fondation de l''Orangerie (Coll?ge de France) for individual Philanthropy and its donors. Additional support has been received from the Royal Society and the ERC (Grant no. 277757). The IRCELYON thanks its scientific services.
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All Science Journal Classification (ASJC) codes
- Organic Chemistry