Gram-Scale Synthesis of an Ultrastable 38-Nuclei Copper(I) Alkynide Nanocluster for Unraveling Bifunctional Photocatalysis

Developing earth-abundant single catalysts capable of simultaneously driving redox reactions is highly desirable, yet it remains elusive due to band gap engineering complexity and rapid charge recombination. Herein, gram-scale synthesis of an ultrastable copper(I) alkynyl nanocluster (<b>Cu38</b>) was realized, and its bifunctionalization was comprehensively studied. <b>Cu38</b> features a sandwiched structure comprising two Cu₁₀ units and a peanut-like Cu₁₈ unit at the waist. Two types of <i>in-situ</i> reactions involving the oxidization of phenylphosphinic acid and the release of C₂^2- ions from alkynol, occur in this assembly system. The stepwise assembly process of <b>Cu38</b> was revealed through mass spectrometry. Catalysis studies reveal that <b>Cu38</b> realizes synchronous photocatalysis disposal in the binary Cr^VI/dye system due to its appropriate band gap and efficient carrier separation, which are further corroborated by density functional theory (DFT) calculations. This work provides strategic guidance for constructing ultrastable high-nuclearity Cu^I nanoclusters and new insights into achieving multiple catalytic half-reactions using redox-type nanoclusters.