We developed a user-friendly method for growing polymer brushes on various substrates in the presence of air by O2-SI-RAFT polymerization and mussel-inspired surface chemistry. In particular, PHEMA brushes grew to 856 nm on the titanium substrate.

Alternating ring-opening copolymerization (ROCOP) is a versatile synthetic method for preparing polyesters using relatively inexpensive and readily available monomers, epoxides and cyclic anhydrides. In this study, a new type of titanium (IV) complex coordinated with iminophenolate ligands was developed as an efficient catalyst for alternating ROCOP. As found in the crystal structures, iminophenolate titanium (IV) complexes exhibited octahedral geometries owing to geometrical con-straints. Electronic tuning of iminophenolate ligands revealed that chloro-substituted ligands are more efficient than other ligands with electron-withdrawing or electron-donating ligands. Density functional theory computation provided reaction profiles where octahedral intermediates and transition states were stabilized, and the chlorine substituent was the most efficient in stabilizing the transition state for the epoxide opening step.