Multivariate metal-organic framework MTV-MIL-101 via post-synthetic cation exchange: is it truly achievable?

The post-synthetic exchange (PSE) method is a well-proven route to replace, modify, and add different functionalities to metal-organic frameworks (MOFs). Particularly, the solvent-assisted cation substitution (SACS) technique has been reported to prepare mixed-metal multivariate metal-organic frameworks (MTV-MOFs). However, such a technique does not apply to all types of MOFs. In 2013, Szilágyi et al. reported the achievement of the mixed-metal MTV-MIL-101 framework via PSE. Since then, a debate has been taking place about the validity of these findings. On the other hand, the attainment of the mixed-metal MIL-101 was reported to be obtainable through the direct synthesis, which is, to some, the only way to achieve it. Here, we settle this dispute by investigating Szilágyi's method not only as described, but also at extended conditions of time and different metal precursors: all attempts were vain. However, by reconsidering the refluxing solvent (dimethylformamide "DMF" instead of water) and the applied reaction conditions (110 °C-20 h), mixed-metal MIL-101(Cr/Fe) was achieved via a simple PSE method.