Phosphorescent Cyclometalated Platinum(II) Enantiomers with Circularly Polarized Luminescence Properties and Their Assembly Behaviors

Abstract

Platinum(II) complexes as supramolecular luminescent materials have received considerable attention due to their unique planar structures and fascinating photophysical properties. However, the molecular design of platinum(II) complexes with impressive circularly polarized luminescence properties still remains challenging and rarely explored. Herein, we reported a series of cyclometalated platinum(II) complexes with benzaldehyde and its derived imine-containing alkynyl ligands to investigate their phosphorescent, chiroptical, and self-assembly behaviors. An isodesmic growth mechanism is found for their temperature-dependent self-assembly process. The chiral sense of the enantiomers can be transferred from the chiral alkynyl ligands to the cyclometalated platinum(II) dipyridylbenzene N^C^N chromophore and further amplified through supramolecular assembly via intermolecular noncovalent interactions. Notably, distinctive phosphorescent properties and nanostructured morphologies have been found for enantiomers 4R and 4S. Their intriguing self-assembled nanostructures and phosphorescence behaviors are supported by crystal structure determination, 1H NMR, emission, and UV-vis absorption spectroscopy, scanning electron microscopy, and X-ray powder diffraction studies.