Ligand-Modulated Synthesis of High-Nuclearity Copper Nanoclusters Enables Photocatalytic Functionalization of C–Cl and C–F Bonds

We introduce a BINAP (2,2′-bis(diphenylphosphino)-1,1′-binaphthyl)-assisted, thiolate-driven strategy that enables the ultrafast assembly of a high-nuclearity Cu NCs [Cu₆₃(TBBT)₄₄(CH₃COOCH₃)₂(CH₃CN)₄(CH₃OH)H₁₄]³⁺ (<b>Cu</b>_<b>63</b>).

Notably, BINAP functions as a transient chelating ligand that stabilizes Cu(I), moderates reduction kinetics, and suppresses uncontrolled thiolate polymerization. The resulting <b>Cu</b>_<b>63</b> structure features a 12-atom Cu core capped by a Cu₅₁(TBBT)₄₄ (TBBT: 4-<i>tert</i>-butylbenzenethiol) shell containing well-defined surface vacancy defects that modulate ligand arrangement and electronic structure. <b>Cu</b>_<b>63</b> exhibits a broad absorption tail that extends continuously into the visible region, air stability, and favorable excited-state redox properties.