Aggregation Inducing Reversible Conformational Isomerization of Surface Staple in Au₁₈SR₁₄ Nanoclusters

Abstract

The conformation of molecules and materials is crucial in determining their properties and applications. Here, this work explores the reversible transformation between two distinct conformational isomers in metal nanoclusters. This work demonstrates the successful manipulation of a controllable and reversible isomerization of Au18SR14 within an aqueous solution through two distinct methods: ethanol addition and pH adjustment. The initial driver is the alteration of the solution environment, leading to the aggregation of Au18SR14 protected by ligands with smaller steric hindrance. At the atomic level, the folding mode of the unique Au4SR5 staple underpins the observed structural transformation. The reversal of staple conformation leads to color shifting between green and orange‐red, and tailors a second emission peak at 725 nm originating from charge transfer from the thiolate to the Au9 core. This work not only deepens the understanding of the surface structure and dual‐emission of metal nanoparticles, but also enhances the comprehension of their isomerization.