Isostructural Nanocluster Manipulation Reveals Pivotal Role of One Surface Atom in Click Chemistry

<jats:title>Abstract</jats:title><jats:p>Elucidating single‐atom effects on the fundamental properties of nanoparticles is challenging because single‐atom modifications are typically accompanied by appreciable changes to the overall particle's structure. Herein, we report the synthesis of a [Cu<jats:sub>58</jats:sub>H<jats:sub>20</jats:sub>PET<jats:sub>36</jats:sub>(PPh<jats:sub>3</jats:sub>)<jats:sub>4</jats:sub>]<jats:sup>2+</jats:sup> (<jats:bold>Cu<jats:sub>58</jats:sub></jats:bold>; PET: phenylethanethiolate; PPh<jats:sub>3</jats:sub>: triphenylphosphine) nanocluster—an atomically precise nanoparticle—that can be transformed into the surface‐defective analog [Cu<jats:sub>57</jats:sub>H<jats:sub>20</jats:sub>PET<jats:sub>36</jats:sub>(PPh<jats:sub>3</jats:sub>)<jats:sub>4</jats:sub>]<jats:sup>+</jats:sup> (<jats:bold>Cu<jats:sub>57</jats:sub></jats:bold>). Both nanoclusters are virtually identical, with five concentric metal shells, save for one missing surface copper atom in <jats:bold>Cu<jats:sub>57</jats:sub></jats:bold>. Remarkably, the loss of this single surface atom drastically alters the reactivity of the nanocluster. In contrast to <jats:bold>Cu<jats:sub>58</jats:sub></jats:bold>, <jats:bold>Cu<jats:sub>57</jats:sub></jats:bold> shows promising activity for click chemistry, particularly photoinduced [3+2] azide‐alkyne cycloaddition (AAC), which is attributed to the active catalytic site in <jats:bold>Cu<jats:sub>57</jats:sub></jats:bold> after the removal of one surface copper atom. Our study not only presents a unique system for uncovering the effect of a single‐surface atom modification on nanoparticle properties but also showcases single‐atom surface modification as a powerful means for designing nanoparticle catalysts.</jats:p>