2025-09-10 東京科学大学
図1．バルク固体中における、空孔機構に基づく原子拡散の模式図
＜関連情報＞
- https://www.isct.ac.jp/ja/news/0iuu3hk91rvr
- https://www.isct.ac.jp/plugins/cms/component_download_file.php?type=2&pageId=&contentsId=1&contentsDataId=2212&prevId=&key=78b2e010c8806e55401386f7cb53bd3a.pdf
- https://onlinelibrary.wiley.com/doi/10.1002/anie.202507444
分子金属クラスター錯体における空孔誘起原子拡散 Vacancy-Induced Atomic Diffusion in a Molecular Metal Cluster Complex
Kosuke Iwata, Koshi Miyazawa, Kenta Kurashima, Hiroshige Yamaura, Dr. Bo Zhu, Dr. Yu Tian, Yuta Takahira, Dr. Koji Yamamoto, Dr. Tsubasa Omoda, Dr. Daisuke Hashizume …
Angewandte Chemie International Edition Published: 26 June 2025
DOI:https://doi.org/10.1002/anie.202507444
Graphical Abstract
We report the formation and dynamic behavior of atomic vacancy in an organometallic palladium cluster complex. Variable-temperature NMR analysis and theoretical calculations of the Pd12 cluster [Pd12(C7H7)6][B(ArF)4]2 suggest that an atomic vacancy migrates rapidly at the surface of the metal cluster on the NMR timescale, leading to the vacancy-induced atomic diffusion in a molecule.
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 Pd12 cluster complex [Pd12(C7H7)6][B(ArF)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 Pd12 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.
