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Rhodium Carbonyl Complexes within the Tunable Microenvironments of UiO-66 Analogues
Rashid G Siddique1, Thomas E Anthony1, Jack D Evans1
1School of Physics, Chemistry and Earth Sciences, University of Adelaide, Adelaide, SA 5005, Australia.
Abstract:
Herein, UiO-66 variants with varying microenvironments were prepared to investigate their influence on the chemistry of Rh carbonyl complexes bound to vacant MOF node sites. The complexity observed in Rh carbonyl-supported species across different UiO-66 variants prompted detailed structural characterization, including defect site analysis. Metal loading was found to be governed by three main factors: the defect content, type of metal node, and nature of functional groups on the linkers. We identified monomeric gem-Rh(CO)2 and dimeric [Rh2(μ-Cl)2(CO)4] species supported on the node as the main entities with varying concentrations of both species and slight shifts in CO stretches in different UiO-66 variants, indicating subtle changes in their electronic environments. The dimeric Rh species was found to be sensitive to moisture, and in UiO-66-NH2 and UiO-66-(OH)2, additional Rh carbonyl species were observed, with no dimeric Rh species being observed when the amine-functionalized support was used. Rh-loaded Ce-UiO-66, UiO-66, and UiO-66-NH2 were exposed to syngas at 100 °C for 3 h. While no significant changes were observed for others, Rh bound within Ce-UiO-66 underwent a change in speciation, with a Rh6(CO)16 cluster becoming the dominant species. These studies demonstrated significant complexity in using UiO-66 topology MOFs as "privileged ligands" for supporting potential heterogeneous catalysts.
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