Vacancy‐Induced Atomic Diffusion in a Molecular Metal Cluster Complex
Abstract
Abstract The presence of atomic vacancies in a close‐packed material is believed to allow the migration of atoms adjacent to the vacancies, which induces dynamics of atoms. However, it is not known whether atoms in discrete molecules can undergo vacancy‐induced dynamics. We describe herein the generation of a close‐packed Pd 12 cluster complex [Pd 12 (C 7 H 7 ) 6 ][B(Ar F ) 4 ] n ( n = 2, 3) with a Pd‐atom vacancy, and the observation of the diffusion of Pd atoms. Variable‐temperature NMR analysis, X‐ray structure analysis, and theoretical calculations indicate that an atomic vacancy is located at the surface sites of the Pd 12 core, and that it migrates rapidly on the NMR timescale. This means that all 11 palladium atoms at the surface undergo self‐diffusion with a low energy barrier. These results demonstrate, for the first time, that atomic diffusion occurs within a molecule through the vacancy mechanism.
Article Details
Authors (12)
Kosuke Iwata
Department of Chemical Science and Engineering School of Materials and Chemical Technology, Institute of Science Tokyo O‐okayama Meguro‐ku Tokyo 152‐8552 Japan
Koshi Miyazawa
Department of Chemical Science and Engineering School of Materials and Chemical Technology, Institute of Science Tokyo O‐okayama Meguro‐ku Tokyo 152‐8552 Japan
Kenta Kurashima
Department of Chemical Science and Engineering School of Materials and Chemical Technology, Institute of Science Tokyo O‐okayama Meguro‐ku Tokyo 152‐8552 Japan
Hiroshige Yamaura
Department of Chemical Science and Engineering School of Materials and Chemical Technology, Institute of Science Tokyo O‐okayama Meguro‐ku Tokyo 152‐8552 Japan
Bo Zhu
Yu Tian
Yuta Takahira
Department of Chemical Science and Engineering School of Materials and Chemical Technology, Institute of Science Tokyo O‐okayama Meguro‐ku Tokyo 152‐8552 Japan
Koji Yamamoto
Tsubasa Omoda
Department of Chemical Science and Engineering School of Materials and Chemical Technology, Institute of Science Tokyo O‐okayama Meguro‐ku Tokyo 152‐8552 Japan
Daisuke Hashizume
RIKEN Center for Emergent Matter Science (CEMS), 2-1 Hirosawa, Wako-shi, Saitama 351-0198, Japan
Shigeyoshi Sakaki
Institute for Integrated Cell-Material Sciences, Rhom Plaza R312, Kyoto University, Kyotodaigaku-Katsura, Nishikyo-ku, Kyoto 615-8246, Japan
Tetsuro Murahashi
Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Institute of Science Tokyo, S1-23, O-okayama, Meguro-ku, Tokyo 152-8552, Japan