[Ag23Pd2(PPh3)10Cl7]0: A new family of synthesizable bi-icosahedral superatomic molecules

Sakiat Hossain; Sayuri Miyajima; Takeshi Iwasa; Ryo Kaneko; Taishu Sekine; Ayaka Ikeda; Tokuhisa Kawawaki; Tetsuya Taketsugu; Yuichi Negishi

doi:10.1063/5.0057005

[Ag₂₃Pd₂(PPh₃)₁₀Cl₇]⁰: A new family of synthesizable bi-icosahedral superatomic molecules

J Chem Phys. 2021 Jul 14;155(2):024302. doi: 10.1063/5.0057005.

Authors

Sakiat Hossain¹, Sayuri Miyajima², Takeshi Iwasa³, Ryo Kaneko², Taishu Sekine², Ayaka Ikeda², Tokuhisa Kawawaki¹, Tetsuya Taketsugu³, Yuichi Negishi¹

Affiliations

¹ Research Institute for Science and Technology, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
² Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, Kagurazaka, Shinjuku-ku 162-8601, Japan.
³ Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Hokkaido 060-0810, Japan.

PMID: 34266257
DOI: 10.1063/5.0057005

Abstract

Icosahedral noble-metal 13-atom nanoclusters (NCs) can form connected structures, which can be regarded as superatomic molecules, by vertex sharing. However, there have been very few reports on the superatomic molecules formed using silver (Ag) as the base element. In this study, we synthesized [Ag₂₃Pd₂(PPh₃)₁₀Cl₇]⁰ (Pd = palladium, PPh₃ = triphenylphosphine, Cl = chloride), in which two icosahedral 13-atom NCs are connected, and elucidated its geometric and electronic structures to clarify what type of superatomic molecules can be synthesized. The results revealed that [Ag₂₃Pd₂(PPh₃)₁₀Cl₇]⁰ is a synthesizable superatomic molecule. Single crystal x-ray diffraction analysis showed that the metal-metal distances in and between the icosahedral structures of [Ag₂₃Pd₂(PPh₃)₁₀Cl₇]⁰ are slightly shorter than those of previously reported [Ag₂₃Pt₂(PPh₃)₁₀Cl₇]⁰, whereas the metal-PPh₃ distances are slightly longer. On the basis of several experiments and density functional theory calculations, we concluded that [Ag₂₃Pd₂(PPh₃)₁₀Cl₇]⁰ and previously reported [Ag₂₃Pt₂(PPh₃)₁₀Cl₇]⁰ are more stable than [Ag₂₅(PPh₃)₁₀Cl₇]²⁺ because of their stronger superatomic frameworks (metal cores). These findings are expected to lead to clear design guidelines for creation of new superatomic molecules.