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Alkynyl-Protected Chiral Bimetallic Ag22Cu7 Superatom with Multiple Chirality Origins |
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| Authors: | Dr Guocheng Deng Kangjae Lee Hongwen Deng Dr Sami Malola Dr Megalamane S Bootharaju Prof Hannu Häkkinen Prof Nanfeng Zheng Prof Taeghwan Hyeon |
| Institution: | 1. Center for Nanoparticle Research, Institute for Basic Science (IBS), School of Chemical and Biological Engineering, and Institute of Chemical Processes, Seoul National University, Seoul, 08826 Republic of Korea
These authors contributed equally to this work.;2. Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and National & Local Joint Engineering Research Center of Preparation Technology of Nanomaterials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China These authors contributed equally to this work.;3. Departments of Physics and Chemistry, Nanoscience Center, University of Jyväskylä, 40014 Jyväskylä, Finland;4. Center for Nanoparticle Research, Institute for Basic Science (IBS), School of Chemical and Biological Engineering, and Institute of Chemical Processes, Seoul National University, Seoul, 08826 Republic of Korea;5. Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and National & Local Joint Engineering Research Center of Preparation Technology of Nanomaterials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China |
| Abstract: | Understanding the origin of chirality in the nanostructured materials is essential for chiroptical and catalytic applications. Here we report a chiral AgCu superatomic cluster, Ag22Cu7(C≡CR)16(PPh3)5Cl6](PPh4), Ag22Cu7 , protected by an achiral alkynyl ligand (HC≡CR: 3,5-bis(trifluoromethyl)phenylacetylene). Its crystal structure comprises a rare interpenetrating biicosahedral Ag17Cu2 core, which is stabilized by four different types of motifs: one Cu(C≡CR)2, four −C≡CR, two chlorides and one helical Ag5Cu4(C≡CR)10(PPh3)5Cl4. Structural analysis reveals that Ag22Cu7 exhibits multiple chirality origins, including the metal core, the metal-ligand interface and the ligand layer. Furthermore, the circular dichroism spectra of R/S-Ag22Cu7 are obtained by employing appropriate chiral molecules as optical enrichment agents. DFT calculations show that Ag22Cu7 is an eight-electron superatom, confirm that the cluster is chirally active, and help to analyze the origins of the circular dichroism. |
| Keywords: | Alkynyl Ligand Bimetallic Cluster Chirality Chirality Origins Superatom |