In:
Angewandte Chemie, Wiley, Vol. 131, No. 35 ( 2019-08-26), p. 12271-12276
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(CH 3 OH) 2 (18‐crown‐6)] + [Cu 5 (S t Bu) 6 ] − ( 1⋅CH 3 OH ) in the chiral space group was prepared, in which the chiral red‐emissive anionic [Cu 5 (S t Bu) 6 ] − cluster was arranged along a twofold screw axis. Interestingly, the release of the coordinated CH 3 OH of the cationic units turned the chiral 1⋅CH 3 OH crystal into a mesomeric crystal [K(18‐crown‐6)] + [Cu 5 (S t Bu) 6 ] − ( 1 ), which has a centrosymmetric space group, by adding symmetry elements of glide and mirror planes through both disordered [Cu 5 (S t Bu) 6 ] − units. The switchable chiral/achiral rearrangement of [Cu 5 (S t Bu) 6 ] − clusters along with the capture/release of CH 3 OH 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)] + [Cu 5 (S t Bu) 6 ] − ( d / l ‐Cu 5V ), which display impressive circularly polarized luminescence (CPL) in contrast to the CPL‐silent racemic mixture of 1⋅CH 3 OH and mesomeric 1 .
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v131.35
DOI:
10.1002/ange.201906614
Language:
English
Publisher:
Wiley
Publication Date:
2019
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