Expanding Clickable Nanocluster Chemistry: Azide‐Functionalized Au ₁₄₄ (SR) ₆₀

Thiolate‐protected Au 144 nanoclusters (NCs) are an intriguing member of the gold NC family. Their geometric structure, distinct electrochemical features, and susceptibility to structural rearrangement under the duress of ligand exchange have been studied, but there are currently no established protocols for surface modification or tuning of their ligand shells post‐assembly. Here, we report the direct synthesis of three regioisomers of azide‐modified Au 144 NCs with 60 azide moieties, i.e., Au 144 (SC 2 H 4 C 6 H 4 ‐N 3 ) 60 , in which the azide functionality is located at the ortho ‐, meta ‐, or para position of the ligand’s phenyl ring. A proof‐of‐concept nanocluster surface strain‐promoted alkyne‐azide cycloaddition (CS‐SPAAC) reaction is also demonstrated, revealing that all 60 azides can be accessible in the para derivative. The CS‐SPAAC chemistry was extended to append a functional TEMPO group, which can be utilized towards an alcohol electro‐oxidation application, to highlight the potential of CS‐SPAAC reactions with azide‐modified Au 144 NCs.