Aromatic donor–acceptor interaction as the driving force to assemble cooperative catalysts is described. Pyrene/naphthalenediimide functionalized Co­(III)-salen complexes self-assembled into bimetallic catalysts through aromatic donor–acceptor interactions and showed high catalytic activity and selectivity in the asymmetric ring opening of various epoxides. Control experiments, nuclear magnetic resonance (NMR) spectroscopy titrations, mass spectrometry measurement, and X-ray crystal structure analysis confirmed that the catalysts assembled based on the aromatic donor–acceptor interaction, which can be a valuable noncovalent interaction in supramolecular catalyst development.

The catalyst activity of bis-acceptor functionalized Co(iii)–salen in hydrolytic kinetic resolution can be fine-tuned by introducing a proper donor compound.