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Updated: Jun 11, 2025
Synthesis and Characterization of Amphiphilic Gold Nanoparticles
Published on: July 2, 2019
Resonance Effects from Substituents on L-Type Ligands Mediate Synthetic Control of Gold Nanocluster Frontier Orbital
Hanna Morales Hernández1, Satoshi Ohtsuka1,2, Arshad Mehmood2,3
1Department of Chemistry, Stony Brook University, Stony Brook, New York 11794, United States.
Abstract:
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 para- and meta-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 para-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.
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