Atomically precise copper dopants in metal clusters boost up stability, fluorescence, and photocatalytic activity.

The structurally precise alloy nanoclusters have been emerged as a burgeoning nanomaterial for their unique physical/chemical features. We here report a rod-like nanocluster [Au 12 Cu 13 (PPh 3 ) 10 I 7 ](SbF 6 ) 2 (Au 12 Cu 13 ), which was generated through a transformation of a [Au 9 (PPh 3 ) 8 ] 3+ intermediate in the presence of CuI, unveiled by time-dependent UV-vis spectroscopy, electrospray ionization mass spectrometry as well as single crystal X-ray diffraction. Au 12 Cu 13 is comprised of two pentagonal bipyramids Au 6 Cu units and a pentagonal prism Cu 11 unit, where the copper and gold species are presented in +1 and 0 chemical states. The Cu-dopants significantly improved the stability and fluorescence (quantum yield: ~34%, 34-folds of homo-Au 25 (PPh 3 ) 10 Br 7 ). The high stability of Au 12 Cu 13 is attributed to the high binding energy of iodine ligands, Au-Cu synergistic effects and its 16-electon system as an 8-electron superatom dimer. Finally, the robust Au 12 Cu 13 exhibited high catalytic activity (~92% conversion and ~84% methyl formate-selectivity) and good durability in methanol photo-oxidation.