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Enantioseparation and chiral induction in Ag29 nanoclusters with intrinsic chirality†

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dc.contributor.author Yoshida, Hiroto
dc.contributor.author Ehara, Masahiro
dc.contributor.author Priyakumar, U. Deva
dc.contributor.author Kawai, Tsuyoshi
dc.contributor.author Nakashima, Takuya
dc.date.accessioned 2020-09-07T07:25:01Z
dc.date.available 2020-09-07T07:25:01Z
dc.date.issued 2020-01-20
dc.identifier.uri http://hdl.handle.net/10061/14047
dc.description.abstract The optical activity of a metal nanocluster (NC) is induced either by an asymmetric arrangement of constituents or by a dissymmetric field of a chiral ligand layer. Herein, we unveil the origin of chirality in Ag29 NCs, which is attributed to the intrinsically chiral atomic arrangement. The X-ray crystal structure of a Ag29(BDT)12(TPP)4 NC (BDT: 1,3-benzenedithiol; TPP: triphenylphosphine) manifested the presence of intrinsic chirality in the outer shell capping the icosahedral achiral Ag13 core. The enantiomers of the Ag29(BDT)12(TPP)4 NC are separated by high-performance liquid chromatography (HPLC) using a chiral column for the first time, showing mirror-image circular dichroism (CD) spectra. The CD spectra are reproduced by time-dependent density functional theory (TDDFT) calculations based on enantiomeric Ag29 models with achiral 1,3-propanedithiolate ligands. The mechanism of chiral induction in the synthesis of Ag29(DHLA)12 (DHLA: α-dihydrolipoic acid) NCs with a chiral ligand system is further discussed with the aid of DFT calculations. The use of the enantiomeric DHLA ligand preferentially leads to a one-handed atomic arrangement which is more stable than the opposite one, inducing the enantiomeric excess in the population of intrinsically chiral Ag29 NCs with CD activity. ja_JP
dc.language.iso en ja_JP
dc.publisher Royal Society of Chemistry ja_JP
dc.relation.isreplacedby https://pubs.rsc.org/en/content/articlelanding/2020/SC/C9SC05299B#!divAbstract ja_JP
dc.rights © The Royal Society of Chemistry 2020 ja_JP
dc.title Enantioseparation and chiral induction in Ag29 nanoclusters with intrinsic chirality† ja_JP
dc.type.nii Journal Article ja_JP
dc.contributor.transcription ヨシダ, ヒロト
dc.contributor.transcription カワイ, ツヨシ
dc.contributor.transcription ナカシマ, タクヤ
dc.contributor.alternative 吉田, 裕斗
dc.contributor.alternative 河合, 壯
dc.contributor.alternative 中嶋, 琢也
dc.textversion none ja_JP
dc.identifier.eissn 2041-6539
dc.identifier.jtitle Chemical Science ja_JP
dc.identifier.issue 9 ja_JP
dc.identifier.spage 2394 ja_JP
dc.identifier.epage 2400 ja_JP
dc.relation.doi 10.1039/C9SC05299B ja_JP
dc.identifier.NAIST-ID 85625960 ja_JP
dc.identifier.NAIST-ID 73293342 ja_JP
dc.identifier.NAIST-ID 73293359 ja_JP

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