How to functionalise metal–organic frameworks to enable guest nanocluster embedment

We report on the development and verification of an enhanced computational model capable of robust predictions and yielding a single descriptor to the successful embedding of guest nanoclusters into the pores of functionalised metal-organic frameworks. Using the predictions of this model, we have been able to embed Pd nanoclusters in the pores of Br-UiO-66 and show that the embedding of Pd nanoclusters in both (OH)2-UiO-66 and (Cl)2-UiO-66 is not successful. Also, using various independent methods, we identified the strong host-guest interactions that anchor the guest nanoclusters inside the Br-UiO-66 framework which result in the surface modification of said nanoclusters. We demonstrated that the level of this surface modification is a direct function of the framework functional groups. This new approach for the rational design of nanocluster-metal-organic framework systems, and a demonstrated tool box for their characterisation, will promote the exploitation of surface modification of nanoclusters via their embedding into functionalised metal-organic framework pores