Abstract
Neighboring group assisted rearrangement substantially increases relaxation rates in dynamic covalent networks, allowing easier (re)processing of these materials. In this work, we introduce a dynamic covalent network with anionic phosphate diesters as the sole dynamic group, incorporating β-hydroxy groups as a neighboring group, mimicking the self-cleaving backbone structure of RNA. The diester-based networks have slightly slower dynamics, but significantly better hydrolytic (and thermal) stability than analogous phosphate triester-based networks. Catalysis by the β-hydroxy group is vital for fast network rearrangement to occur, while the nature of the counterion has a negligible effect on the relaxation rate. Variable temperature (31)P solid-state NMR demonstrated a dissociative bond rearrangement mechanism to be operative.