Cations Controlling the Chiral Assembly of Luminescent Atomically Precise Copper(I) Clusters
1College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, 450001, China.
Angewandte Chemie (International Ed. in English)
|July 4, 2019
Summary
Chiral copper clusters can be controllably assembled and disassembled, switching between chiral and achiral states. This transformation, driven by methanol capture and release, modulates luminescence and enables circularly polarized luminescence.
Area of Science:
- Coordination Chemistry
- Supramolecular Chemistry
- Materials Science
Background:
- Chiral metal clusters are essential for developing advanced chiroptical materials.
- Controlling the assembly and disassembly of chiral clusters is key to tuning their properties.
Purpose of the Study:
- To investigate the chiral assembly of copper clusters and their chiroptical properties.
- To explore the switchable chiral/achiral rearrangement of copper clusters.
- To achieve controllable luminescence and circularly polarized luminescence (CPL).
Main Methods:
- Preparation of a racemic mixture of a chiral copper cluster complex: [K(CH3OH)2(18-crown-6)]+ [Cu5(StBu)6]- (1·CH3OH).
- Induction of chiral assembly using cationic chiral amino alcohols to form enantiomeric pairs: [d/l-valinol(18-crown-6)]+ [Cu5(StBu)6]- (d/l-Cu5V).
- Analysis of crystal structures, luminescence, and CPL properties.
Main Results:
- A switchable chiral/achiral rearrangement of [Cu5(StBu)6]- clusters was achieved through the capture and release of methanol.
- This rearrangement altered the crystal symmetry from chiral to centrosymmetric and vice versa.
- The chiral assembly using amino alcohols resulted in impressive CPL, unlike the CPL-silent racemic or achiral forms.
Conclusions:
- The study demonstrates a novel method for controlling the chiral assembly and chiroptical properties of metal clusters.
- The methanol-induced switchable chiral/achiral transformation offers a new pathway for designing responsive luminescent materials.
- The development of CPL-active copper clusters opens avenues for applications in chiral sensing and optoelectronics.
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