Enantioseparation of Au 20 (PP 3 ) 4 Cl 4 Clusters with Intrinsically Chiral Cores.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION(2018)

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摘要
Au-20(PP3)(4)Cl-4 (PP3=tris(2-(diphenylphosphino)ethyl) phosphine), abbreviated as Au-20, is the only Au nanocluster with an intrinsically chiral core without a chiral environment (chiral ligands or Au-thiolate staples), making it a unique object to understand chiral evolution and explore chiral applications. Unfortunately, the synthesized Au-20 is racemic, and its enantiomers have not yet been separated. Herein, we report a supramolecular assembly strategy with -cyclodextrin (-CD) to afford enantiopure Au-20 in bulk, and an enantiomer excess (ee) value of as-separated Au-20 of 97%. As a result of its high purity, the distinctive optical activity of Au-20, which originates from electronic transitions confined in chiral cores, is fully explored. Theoretical studies reveals that the enantioseparation results from the preferential self-assembly of -CD with organic ligands on the surface of right-handed Au-20.
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关键词
chirality,cyclodextrins,gold,nanoclusters,supramolecular chemistry
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