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Revealing the chirality origin and homochirality crystallization of Ag14 nanocluster at the molecular level
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Revealing the chirality origin and homochirality crystallization of Ag14 nanocluster at the molecular level
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Journal Article
Revealing the chirality origin and homochirality crystallization of Ag14 nanocluster at the molecular level
2021
Overview
Although chirality is an ever-present characteristic in biology and some artificial molecules, controlling the chirality and demystifying the chirality origin of complex assemblies remain challenging. Herein, we report two homochiral Ag
14
nanoclusters with inherent chirality originated from identical rotation of six square faces on a Ag
8
cube driven by intra-cluster π···π stacking interaction between pntp
−
(Hpntp =
p-
nitrothiophenol) ligands. The spontaneous resolution of the racemic (SD/
rac
-Ag14a) to homochiral nanoclusters (SD/
L
-Ag14 and SD/
R
-Ag14) can be realized by re-crystallizing SD/
rac
-Ag14a in acetonitrile, which promotes the homochiral crystallization in solid state by forming C–H···O/N hydrogen bonds with nitro oxygen atoms in pntp
−
or aromatic hydrogen atoms in dpph (dpph = 1,6-bis(diphenylphosphino)hexane) on Ag
14
nanocluster. This work not only provides strategic guidance for the syntheses of chiral silver nanoclusters in an all-achiral environment, but also deciphers the origin of chirality at molecular level by identifying the special effects of intra- and inter-cluster supramolecular interactions.
The preparation of chiral monolayer-protected metal clusters is interesting for their potential applications in a variety of fields, including catalysis. Here, the authors synthesize chiral Ag
14
nanoclusters in an all-achiral environment, and decipher the origin of chirality at the molecular level; the solvent choice is key to achieve homochiral crystallization.
