Iwata Kosuke, Miyazawa Koshi, Kurashima Kenta, Yamaura Hiroshige, Zhu Bo, Tian Yu, Takahira Yuta, Yamamoto Koji, Omoda Tsubasa, Hashizume Daisuke, Sakaki Shigeyoshi, Murahashi Tetsuro
Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Institute of Science Tokyo, O-okayama, Meguro-ku, Tokyo, 152-8552, Japan.
Institute of Functional Materials Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun, 130024, P.R. China.
Angew Chem Int Ed Engl. 2025 Aug 25;64(35):e202507444. doi: 10.1002/anie.202507444. Epub 2025 Jul 9.
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 cluster complex [Pd(CH)][B(Ar)] (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 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.
人们认为，密堆积材料中原子空位的存在会使空位附近的原子发生迁移，从而引发原子动力学。然而，尚不清楚离散分子中的原子是否能经历空位诱导的动力学过程。我们在此描述了一种具有钯原子空位的密堆积钯簇配合物[Pd(CH)][B(Ar)]（n = 2, 3）的生成，以及钯原子扩散的观测。变温核磁共振分析、X射线结构分析和理论计算表明，一个原子空位位于钯核的表面位点，并且它在核磁共振时间尺度上快速迁移。这意味着表面的所有11个钯原子都以低能垒进行自扩散。这些结果首次证明，原子通过空位机制在分子内发生扩散。
