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Electronic Control of Emission Behavior in Atomically Precise Copper Nanoclusters.
Maho Kamiyama1, Linlin Zeng2, Milan Kumar Jena3,4
1Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira 2-1-1, Aoba-ku, Sendai 980-8577, Japan.
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.
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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.