Helical Assemblies of Colloidal Nanocrystals with Long-Range Order and Their Fusion into Continuous Structures

J Am Chem Soc. 2025 Jan 7. doi: 10.1021/jacs.4c13831. Online ahead of print.

Abstract

Chirality epitomizes the sophistication of chemistry, representing some of its most remarkable achievements. Yet, the precise synthesis of chiral structures from achiral building blocks remains a profound and enduring challenge in synthetic chemistry and materials science. Here, we demonstrate that achiral colloidal nanocrystals, including Au and Ag nanocrystals, can assemble into long-range-ordered helical assemblies with the assistance of chiral molecules. The synchronized aggregation kinetics between colloidal silver or gold nanocrystals and π-conjugated perylene diimide molecules enables the nanocrystals to precisely follow the helical pathways of the molecular assemblies. This results in the formation of helical nanocrystal assemblies extending over tens of micrometers. These helically organized nanocrystals, exhibiting high positional precision, display linear size-dependent chiroptical properties. Furthermore, more intricate helical assemblies, featuring triple, quadruple, and quintuple nanocrystal strands, can be observed in addition to the commonly encountered double helical assemblies. Finally, these helical assemblies, composed of discrete Ag nanocrystals, can fuse into continuous Ag2S helical structures following a sulfidation reaction, ultimately leading to the formation of diverse metal sulfide helices through cation exchange processes.