Anions- and Solvents-Triggered Reversible Interconversion in Silver Nanocluster and Their Assembly

Atomic-precision nanoclusters have emerged as a pivotal frontier in nanotechnology, attributed to their exceptional structural transformation and assembly capabilities. Silver-based nanoclusters are characterized by their adjustable structures and properties that are susceptible to environmental influences, which render them an ideal platform for functional modifications. This study reports the synthesis of the green [Ag₂₇(SAdm)₁₂(DPPP)₂(F₃C₂O₂)₆]Cl nanocluster stabilized by 1,3-bis(diphenylphosphine)propane and 1-adamantanethiol. Upon the introduction of F₃CSO₃⁻ ions, these nanoclusters undergo transformation to form the red [Ag₂₇(SAdm)₁₂(DPPP)₃(F₃C₂O₂)₃Cl₂](F₃CSO₃). Notably, the two nanoclusters separately exhibit interconversion with [Ag₂₃(SAdm)₁₂]³⁺: they transform into [Ag₂₃(SAdm)₁₂]³⁺ in polar solvents and revert to the corresponding Ag₂₇ nanoclusters in nonpolar solvents. Furthermore, when [Ag₂₃(SAdm)₁₂]³⁺ interacts with ClO₄⁻ ions, it self-assembles into a three-dimensional framework structure of [Ag₂₃(SAdm)₁₂](ClO₄)₃, exhibiting pronounced photoluminescence. This work sheds light on understanding the ion- and solvent-induced cluster transformation and assembly mechanisms, which will facilitate the investigation of metal nanoclusters or even nanoparticles containing various ions in various solvent systems.