Mechanism Insight into the Constitutional Phase Change Selection of Dynameric Framework Libraries

We show that the use of reversibly connected trialdehyde cores and diamine hydrophilic/hydrophobic connectors may generate libraries of dynameric frameworks of variable composition. The dynamic reversible imine- and trans-imination reactions induce the progressive segregation of libraries consisting of homo- and heterodynameric frameworks through the constitutional selection and successive precipitation of low-soluble hydrophobic films and hydrophilic/hydrophobic core-shell particles. This "precipitation-driven segregation" results in the formation of membrane with unique asymmetric morpholgy. Systematic compositional changes of dynamers, segregating solvents, and casting surfaces were correlated with the emerged membrane structure, and NMR/transmission electron microscopy-energy-dispersive X-ray characterizations mostly supported their hypothesis.