Smart Reversible Transformations between Chiral Superstructures of Copper Clusters for Optical and Chiroptical Switching.

Abstract

Superstructures made from nanoscale clusters with new collective properties are promising in high-tech applications; however, chiral superstructures remain elusive, and the limited intercluster coupling effect at room temperature hampers the tailoring of collective properties. Here, we show that from chiral monomeric copper clusters to two enantiomeric pairs of supercrystals with distinct phases, the absorption band edge red-shifts by over 1.3 eV, with photoluminescence and circularly polarized phosphorescence from visible (572 nm) to near-infrared (NIR, 858 nm). These supercrystals with high NIR quantum yields of up to 45% at room temperature are prototyped for night-vision imaging. In response to solvent and temperature stimuli, chiral supercrystal-to-supercrystal transformations occurred, concomitant with high-contrast optical/chiroptical switching. In situ single-crystal X-ray diffraction (SCXRD), steady-state and time-resolved optical spectroscopy, and response experiments combined with theoretical calculations demonstrate that distance-sensitive intercluster orbital interactions contribute to the exceptional collective optical responses. Such chiral supercrystals built from subnanoscale metal clusters with novel collective chiroptical responses would be useful in the fields of information storage and NIR optical devices.