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Smart Reversible Transformations between Chiral Superstructures of Copper Clusters for Optical and Chiroptical
Zhen Han1, Yubing Si1, Xi-Yan Dong1,2
1Henan Key Laboratory of Crystalline Molecular Functional Materials, and College of Chemistry, Zhengzhou University, Zhengzhou 450001, China.
Journal of the American Chemical Society
|March 13, 2023
Summary
Researchers developed chiral supercrystals from copper clusters, achieving significant optical property shifts and near-infrared emission for night-vision imaging. These materials exhibit stimuli-responsive transformations and potential for advanced optical devices.
Area of Science:
- Materials Science
- Nanotechnology
- Optoelectronics
Background:
- Chiral superstructures are crucial for advanced applications but remain challenging to create.
- Limited intercluster coupling at room temperature restricts the control over collective properties.
Purpose of the Study:
- To synthesize and characterize novel chiral supercrystals from monomeric copper clusters.
- To investigate the collective optical properties and stimuli-responsive behavior of these supercrystals.
Main Methods:
- Synthesis of chiral monomeric copper clusters and their assembly into supercrystals.
- In situ single-crystal X-ray diffraction (SCXRD) and optical spectroscopy (steady-state and time-resolved).
- Response experiments and theoretical calculations to understand intercluster interactions.
Main Results:
- Achieved a red-shift in absorption band edge by over 1.3 eV.
- Observed photoluminescence and circularly polarized phosphorescence from visible to near-infrared (NIR) regions (572–858 nm).
- Demonstrated high NIR quantum yields (up to 45%) at room temperature and stimuli-responsive supercrystal transformations with optical switching.
Conclusions:
- Chiral supercrystals from subnanoscale metal clusters exhibit unique collective chiroptical responses.
- Distance-sensitive intercluster orbital interactions are key to these optical properties.
- Potential applications in night-vision imaging, information storage, and NIR optical devices.
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