Resonance Effects from Substituents on L-Type Ligands Mediate Synthetic Control of Gold Nanocluster Frontier Orbital Energies

The ligands of metal nanoclusters can be used to control their properties and reactivity, but a framework guiding their use remains elusive. Hammett studies of Au₈(PPh₃)₇²⁺ and Au₉(PPh₃)₈³⁺ nanoclusters with <i>para-</i> and <i>meta</i>-methyl and -methoxy groups indicate that resonance effects, not inductive effects, yield quantitative shifts of the HOMO-LUMO transitions involving orbitals local to the cluster core. Individual ligand exchanges reveal that these shifts are caused by only four of seven ligands, inconsistent with inductive effects. Quantum chemical calculations predict no trend in Au atom charges with respect to Hammett parameter but do predict bond length trends expected for a resonance structure that includes the Au atoms. Computed orbitals show contributions from specific <i>para-</i>OMe oxygen lone pairs to the HOMO, indicating delocalization from the core to specific ligands. These results suggest that resonance structures could be drawn including Au and ligands, guiding efforts to modulate nanocluster electronic structure and energy transfer.