Ligand-Regulated Long-Lived Charge Transfer Dynamics in Atomically Precise Metal Nanoclusters

Area of Science:

• Materials Science
• Photochemistry
• Nanotechnology

Background:

• Ligand-mediated long-lived charge transfer (CT) is key for exciton harvesting in metal nanoclusters (NCs).
• The precise role of ligands in modulating CT dynamics within excited NCs is not fully understood.
• Understanding ligand effects is crucial for optimizing NCs in photocatalysis, photovoltaics, and artificial photosynthesis.

Purpose of the Study:

• To establish principles for ligand engineering that elucidate long-lived CT kinetics in metal NCs.
• To investigate how ligand structure influences charge separation and recombination rates.
• To enhance the light-harvesting efficiency of metal NCs for practical applications.

Main Methods:

• Systematic ligand engineering of metal nanoclusters.
• Kinetic studies of charge transfer dynamics.
• Evaluation of charge separation and recombination rates.
• Assessment of photocatalytic activity and photocurrent generation.

Main Results:

• Bulky ligands were found to significantly reduce the attenuation of charge separation rates.
• Incorporating bulky ligands increased the decay rates of charge recombination.
• Enhanced charge separation efficiency was observed with bulky ligands.
• Metal NCs with bulky ligands showed improved reactive oxygen species generation and photocurrent intensity.

Conclusions:

• Ligand engineering is a critical factor in controlling long-lived CT dynamics in metal NCs.
• Bulky ligands optimize charge separation and recombination kinetics, boosting light-conversion efficiency.
• These findings clarify the impact of ligand size on NC performance and advance their use in energy technologies.