Chirality,the property that an object cannot coincide with its mirror image arising from lack of mirror symmetry,is ubiquitous in nature at various length scales.The physical and chemical properties are strongly relat...Chirality,the property that an object cannot coincide with its mirror image arising from lack of mirror symmetry,is ubiquitous in nature at various length scales.The physical and chemical properties are strongly related to the nature of chiral complexes,playing a significant role in various fields such as photonics,biochemistry,medicine and catalysis.In particular,the recent flexible design of chiral metal nanostructures offers one platform for deeply understanding the origin of chirality and one roadmap for the precise construction of chiral nanomaterials directed by the applications.Herein,we summarize the different geometries and classical synthetic approaches to chiral noble metal nanomaterials.Moreover,chiroptical properties and potential applications of chiral metal nanostructures are discussed as well.Finally,the opportunities and challenges toward the synthesis and application of chiral metal nanostructures are proposed.展开更多
Distortion of planar aromatics occurs in the fused rings conjugated with bulky substituents,which generates racemic enantiomers with high transformation energy barriers.However,direct synthesis of homochiral distorted...Distortion of planar aromatics occurs in the fused rings conjugated with bulky substituents,which generates racemic enantiomers with high transformation energy barriers.However,direct synthesis of homochiral distorted aryl compounds is a very challenging task.Here,we presented a molecular folding strategy to control distorted aryl homochirality.Amino acids and their derivatives conjugated on the polycyclic aromatic hydrocarbons including benzenes,naphthalenes and triphenylenes,which formed parallelβ-sheet arrays through intramolecular hydrogen bonds.The folding behavior enabled distorted or twisted geometry of aromatics,of which the handedness was associated with the absolute chirality of amino acids.X-ray crystallography,theoretical calculations and circular dichroism spectroscopy verified the distorted homochirality in the solid and solution phase.The relatively small rotational barrier between the enantiomers made the molecule sensitive to the environment and thus realized the solvent-controlled chiral inversion.Theβ-sheet folding strategy can be widely used in polycyclic aromatic hydrocarbons with various functions,which provided a promising strategy to control inherent chirality of aromatics with adaptive chiroptical responses.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.22071172,21902148,12205165,50835002 and 51105102)。
文摘Chirality,the property that an object cannot coincide with its mirror image arising from lack of mirror symmetry,is ubiquitous in nature at various length scales.The physical and chemical properties are strongly related to the nature of chiral complexes,playing a significant role in various fields such as photonics,biochemistry,medicine and catalysis.In particular,the recent flexible design of chiral metal nanostructures offers one platform for deeply understanding the origin of chirality and one roadmap for the precise construction of chiral nanomaterials directed by the applications.Herein,we summarize the different geometries and classical synthetic approaches to chiral noble metal nanomaterials.Moreover,chiroptical properties and potential applications of chiral metal nanostructures are discussed as well.Finally,the opportunities and challenges toward the synthesis and application of chiral metal nanostructures are proposed.
基金supported by the National Natural Science Foundation of China(Nos.21901145,22171165)the financial support from Youth cross-scientific innovation group of Shandong University(No.2020QNQT003).
文摘Distortion of planar aromatics occurs in the fused rings conjugated with bulky substituents,which generates racemic enantiomers with high transformation energy barriers.However,direct synthesis of homochiral distorted aryl compounds is a very challenging task.Here,we presented a molecular folding strategy to control distorted aryl homochirality.Amino acids and their derivatives conjugated on the polycyclic aromatic hydrocarbons including benzenes,naphthalenes and triphenylenes,which formed parallelβ-sheet arrays through intramolecular hydrogen bonds.The folding behavior enabled distorted or twisted geometry of aromatics,of which the handedness was associated with the absolute chirality of amino acids.X-ray crystallography,theoretical calculations and circular dichroism spectroscopy verified the distorted homochirality in the solid and solution phase.The relatively small rotational barrier between the enantiomers made the molecule sensitive to the environment and thus realized the solvent-controlled chiral inversion.Theβ-sheet folding strategy can be widely used in polycyclic aromatic hydrocarbons with various functions,which provided a promising strategy to control inherent chirality of aromatics with adaptive chiroptical responses.
基金supported by the National Natural Science Foundation of China (22071226, 51732011, 21431006, 21761132008, 81788101, 11227901 and 11874164)the Funding of University of Science and Technology of China (KY2060000168 and YD2060002013)+2 种基金the Foundation for Innovative Research Groups of the National Natural Science Foundation of China (21521001)the Key Research Program of Frontier Sciences, CAS (QYZDJ-SSW-SLH036)the Users with Excellence and Scientific Research Grant of Hefei Science Center of CAS (2015HSC-UE007)。
