Active Role of Methanol in Post-Synthetic Linker Exchange in the Metal–Organic Framework UiO-66

UiO-66 is known as one of the most robust metal–organic framework materials. Nevertheless, UiO-66 has also been shown to undergo postsynthetic exchange of structural linkers with surprising ease in some solvents. To date, the exchange mechanism has not yet been fully elucidated. Here, we show how time-resolved monitoring grants insight into the selected case of exchanging 2-aminoterephthalate into UiO-66 in methanol. Analysis of both the solid and liquid phases, complemented by computational insights, revealed the active role of methanol in the creation and stabilization of dangling linkers. Similar to monocarboxylate defects that can be introduced during UiO-66 synthesis, such dangling linkers undergo fast exchange. The presence of missing-linker or missing-cluster defects at the start of the exchange process was shown to have no considerable impact on the equilibrium composition. After the exchange process, the incoming 2-aminoterephthalate and remaining terephthalate linkers were distributed homogeneou...