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A Continuous-flow Photocatalytic Reactor for the Precisely Controlled Deposition of Metallic Nanoparticles

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Electronic Control of Emission Behavior in Atomically Precise Copper Nanoclusters.

Maho Kamiyama¹, Linlin Zeng², Milan Kumar Jena^3,4

¹Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira 2-1-1, Aoba-ku, Sendai 980-8577, Japan.

|May 1, 2026

Summary

Ligand positioning in copper nanoclusters (Cu NCs) precisely controls their light emission. This study shows how modifying ligand electronic effects tunes photoluminescence for advanced materials.

Keywords:

copper emission ligands nanocluster photoluminescence

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Area of Science:

Materials Science
Nanotechnology
Quantum Chemistry

Background:

Atomically precise copper nanoclusters (Cu NCs) are crucial for understanding quantum confinement effects.
Isolating ligand electronic effects without altering Cu NC core structure is challenging.

Purpose of the Study:

To investigate how varying ligand substitution position and electronic nature affects Cu NC photoluminescence.
To establish a strategy for controlling emission properties in Cu NCs.

Main Methods:

Synthesized four compositionally identical Cu11 NCs with varied thiolate ligands (methyl- and amino-substituted benzenethiols in para and meta configurations).
Utilized steady-state and time-resolved spectroscopy, transient absorption, and theoretical calculations.
Analyzed ligand-to-metal electronic communication and its impact on excited-state dynamics.

Main Results:

Identical Cu11 NCs with different ligand substitutions showed distinct photoluminescence behaviors.
Ligand substitution modulated excited-state relaxation, triplet-like excited-state stabilization, and oxygen sensitivity.
Cu11-3ABT achieved a 26.1% photoluminescence quantum yield due to enhanced excited-state stabilization.

Conclusions:

Ligand positional engineering is a powerful strategy to control emission dynamics in atomically precise Cu NCs.
This approach provides fundamental insights into Cu NC excited-state physics.
Offers design principles for highly emissive, earth-abundant metal NCs.