Al13− and B@Al12− superatoms on a molecularly decorated substrate

Masahiro Shibuta; Tomoya Inoue; Toshiaki Kamoshida; Toyoaki Eguchi; Atsushi Nakajima

doi:10.1038/s41467-022-29034-9

Al₁₃⁻ and B@Al₁₂⁻ superatoms on a molecularly decorated substrate

Masahiro Shibuta, Tomoya Inoue, Toshiaki Kamoshida, Toyoaki Eguchi, Atsushi Nakajima

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

8 Citations (Scopus)

Abstract

Aluminum nanoclusters (Al_n NCs), particularly Al₁₃⁻ (n = 13), exhibit superatomic behavior with interplay between electron shell closure and geometrical packing in an anionic state. To fabricate superatom (SA) assemblies, substrates decorated with organic molecules can facilitate the optimization of cluster–surface interactions, because the molecularly local interactions for SAs govern the electronic properties via molecular complexation. In this study, Al_n NCs are soft-landed on organic substrates pre-deposited with n-type fullerene (C₆₀) and p-type hexa-tert-butyl-hexa-peri-hexabenzocoronene (HB-HBC, C₆₆H₆₆), and the electronic states of Al_n are characterized by X-ray photoelectron spectroscopy and chemical oxidative measurements. On the C₆₀ substrate, Al_n is fixed to be cationic but highly oxidative; however, on the HB-HBC substrate, they are stably fixed as anionic Al_n⁻ without any oxidations. The results reveal that the careful selection of organic molecules controls the design of assembled materials containing both Al₁₃⁻ and boron-doped B@Al₁₂⁻ SAs through optimizing the cluster–surface interactions.

Original language	English
Article number	1336
Journal	Nature communications
Volume	13
Issue number	1
DOIs	https://doi.org/10.1038/s41467-022-29034-9
Publication status	Published - 2022 Dec

ASJC Scopus subject areas

Chemistry(all)
Biochemistry, Genetics and Molecular Biology(all)
General
Physics and Astronomy(all)

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title = "Al13− and B@Al12− superatoms on a molecularly decorated substrate",

abstract = "Aluminum nanoclusters (Aln NCs), particularly Al13− (n = 13), exhibit superatomic behavior with interplay between electron shell closure and geometrical packing in an anionic state. To fabricate superatom (SA) assemblies, substrates decorated with organic molecules can facilitate the optimization of cluster–surface interactions, because the molecularly local interactions for SAs govern the electronic properties via molecular complexation. In this study, Aln NCs are soft-landed on organic substrates pre-deposited with n-type fullerene (C60) and p-type hexa-tert-butyl-hexa-peri-hexabenzocoronene (HB-HBC, C66H66), and the electronic states of Aln are characterized by X-ray photoelectron spectroscopy and chemical oxidative measurements. On the C60 substrate, Aln is fixed to be cationic but highly oxidative; however, on the HB-HBC substrate, they are stably fixed as anionic Aln− without any oxidations. The results reveal that the careful selection of organic molecules controls the design of assembled materials containing both Al13− and boron-doped B@Al12− SAs through optimizing the cluster–surface interactions.",

author = "Masahiro Shibuta and Tomoya Inoue and Toshiaki Kamoshida and Toyoaki Eguchi and Atsushi Nakajima",

note = "Funding Information: We are grateful to Professor Hideyuki Tsukada (Yokohama City University) for supplying the HB-HBC samples, to Professor Takashi Yokoyama (Yokohama City University) for providing information regarding the molecular deposition of HB-HBC, and to Dr. Hironori Tsunoyama for providing some calculation results. This work is partly supported by JSPS KAKENHI of Grants-in-Aid for Scientific Research (A) No. 19H00890 (A.N.) and Scientific Research (C) No. 18K04942 (M.S.), for Challenging Research Nos. 17H06226(A.N.) and 21K18939 (A.N.), and for Transformative Research Areas (A) “Hyper–Ordered Structures Science” (21H05573) (A.N.). Funding Information: We are grateful to Professor Hideyuki Tsukada (Yokohama City University) for supplying the HB-HBC samples, to Professor Takashi Yokoyama (Yokohama City University) for providing information regarding the molecular deposition of HB-HBC, and to Dr. Hironori Tsunoyama for providing some calculation results. This work is partly supported by JSPS KAKENHI of Grants-in-Aid for Scientific Research (A) No. 19H00890 (A.N.) and Scientific Research (C) No. 18K04942 (M.S.), for Challenging Research Nos. 17H06226(A.N.) and 21K18939 (A.N.), and for Transformative Research Areas (A) “Hyper–Ordered Structures Science” (21H05573) (A.N.). Publisher Copyright: {\textcopyright} 2022, The Author(s).",

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N1 - Funding Information: We are grateful to Professor Hideyuki Tsukada (Yokohama City University) for supplying the HB-HBC samples, to Professor Takashi Yokoyama (Yokohama City University) for providing information regarding the molecular deposition of HB-HBC, and to Dr. Hironori Tsunoyama for providing some calculation results. This work is partly supported by JSPS KAKENHI of Grants-in-Aid for Scientific Research (A) No. 19H00890 (A.N.) and Scientific Research (C) No. 18K04942 (M.S.), for Challenging Research Nos. 17H06226(A.N.) and 21K18939 (A.N.), and for Transformative Research Areas (A) “Hyper–Ordered Structures Science” (21H05573) (A.N.). Funding Information: We are grateful to Professor Hideyuki Tsukada (Yokohama City University) for supplying the HB-HBC samples, to Professor Takashi Yokoyama (Yokohama City University) for providing information regarding the molecular deposition of HB-HBC, and to Dr. Hironori Tsunoyama for providing some calculation results. This work is partly supported by JSPS KAKENHI of Grants-in-Aid for Scientific Research (A) No. 19H00890 (A.N.) and Scientific Research (C) No. 18K04942 (M.S.), for Challenging Research Nos. 17H06226(A.N.) and 21K18939 (A.N.), and for Transformative Research Areas (A) “Hyper–Ordered Structures Science” (21H05573) (A.N.). Publisher Copyright: © 2022, The Author(s).

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N2 - Aluminum nanoclusters (Aln NCs), particularly Al13− (n = 13), exhibit superatomic behavior with interplay between electron shell closure and geometrical packing in an anionic state. To fabricate superatom (SA) assemblies, substrates decorated with organic molecules can facilitate the optimization of cluster–surface interactions, because the molecularly local interactions for SAs govern the electronic properties via molecular complexation. In this study, Aln NCs are soft-landed on organic substrates pre-deposited with n-type fullerene (C60) and p-type hexa-tert-butyl-hexa-peri-hexabenzocoronene (HB-HBC, C66H66), and the electronic states of Aln are characterized by X-ray photoelectron spectroscopy and chemical oxidative measurements. On the C60 substrate, Aln is fixed to be cationic but highly oxidative; however, on the HB-HBC substrate, they are stably fixed as anionic Aln− without any oxidations. The results reveal that the careful selection of organic molecules controls the design of assembled materials containing both Al13− and boron-doped B@Al12− SAs through optimizing the cluster–surface interactions.

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Al₁₃⁻ and B@Al₁₂⁻ superatoms on a molecularly decorated substrate

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