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- Title
Cations Controlling the Chiral Assembly of Luminescent Atomically Precise Copper(I) Clusters.
- Authors
Jin, Yan; Li, Si; Han, Zhen; Yan, Bing‐Jie; Li, Hai‐Yang; Dong, Xi‐Yan; Zang, Shuang‐Quan
- Abstract
Chiral assembly and asymmetric synthesis are critically important for the generation of chiral metal clusters with chiroptical activities. Here, a racemic mixture of [K(CH3OH)2(18‐crown‐6)]+[Cu5(StBu)6]− (1⋅CH3OH) in the chiral space group was prepared, in which the chiral red‐emissive anionic [Cu5(StBu)6]− cluster was arranged along a twofold screw axis. Interestingly, the release of the coordinated CH3OH of the cationic units turned the chiral 1⋅CH3OH crystal into a mesomeric crystal [K(18‐crown‐6)]+[Cu5(StBu)6]− (1), which has a centrosymmetric space group, by adding symmetry elements of glide and mirror planes through both disordered [Cu5(StBu)6]− units. The switchable chiral/achiral rearrangement of [Cu5(StBu)6]− clusters along with the capture/release of CH3OH were concomitant with an intense increase/decrease in luminescence. We also used cationic chiral amino alcohols to induce the chiral assembly of a pair of enantiomers, [d/l‐valinol(18‐crown‐6)]+[Cu5(StBu)6]− (d/l‐Cu5V), which display impressive circularly polarized luminescence (CPL) in contrast to the CPL‐silent racemic mixture of 1⋅CH3OH and mesomeric 1.
- Subjects
METAL clusters; MIRRORS; AMINO alcohols; SPACE groups; COPPER; ASYMMETRIC synthesis; RACEMIC mixtures
- Publication
Angewandte Chemie, 2019, Vol 131, Issue 35, p12271
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201906614