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Milling-Induced "Turn-off" Luminescence in Copper Nanoclusters
Subrata Duary1, Arijit Jana1, Amitabha Das2
1DST Unit of Nanoscience (DST UNS) and Thematic Unit of Excellence (TUE), Department of Chemistry, Indian Institute of Technology, Madras, Chennai 600036, India.
Inorganic Chemistry
|September 25, 2024
Summary
Two new copper nanoclusters (NCs) exhibit mechanoresponsive luminescence, turning off when milled and recovering with solvent vapors. These findings expand the library of luminescent coinage metal NCs for advanced applications.
Area of Science:
- Materials Science
- Nanotechnology
- Photochemistry
Background:
- Atomically precise copper nanoclusters (NCs) are investigated for their strong photoluminescence.
- Applications in photonics, optoelectronics, and sensing require precisely engineered NCs with understood luminescence properties.
Purpose of the Study:
- To report two novel copper nanoclusters, Cu4 and Cu6, with mechanoresponsive luminescence.
- To characterize their structure, luminescence properties, and response to mechanical stimuli.
Main Methods:
- Single-crystal X-ray diffraction for structural determination.
- High-resolution electrospray ionization mass spectrometry for molecular characterization.
- Photoluminescence spectroscopy and lifetime measurements.
Main Results:
- Two copper nanoclusters, [Cu4(MNA)2(DPPE)2] (Cu4) and [Cu6(MNA-H)6] (Cu6), were synthesized and characterized.
- Both Cu4 and Cu6 exhibit "turn-off" mechanoresponsive luminescence, losing emission upon milling and regaining it with solvent vapor exposure.
- Structural analysis revealed distinct Cu-S kernel architectures (flattened boat-shaped Cu4S2 and adamantane-like Cu6S6).
- Average luminescence lifetimes were measured at 0.84 μs for Cu4 and 1.64 μs for Cu6.
Conclusions:
- The study introduces thermally stable, mechanoresponsive luminescent copper nanoclusters.
- These findings contribute to the diversity of coinage metal NCs and their potential applications in responsive materials.
