Takezawa Hiroki, Tamura Yukari, Fujita Makoto
Department of Applied Chemistry, School of Engineering, The University of Tokyo, Mitsui Link Lab Kashiwanoha 1, FS CREATION, 6-6-2 Kashiwanoha, Kashiwa, Chiba, Japan.
Tokyo College, UT Institutes for Advanced Study (UTAIS), The University of Tokyo, Mitsui Link Lab Kashiwanoha 1, FS CREATION, 6-6-2 Kashiwanoha, Kashiwa, Chiba, Japan.
Chemistry. 2025 May 14;31(27):e202500009. doi: 10.1002/chem.202500009. Epub 2025 Apr 8.
The self-assembly process of a double-walled cage formed from a semiflexible tripodal ligand and a Pd(II) 90-degree block was tracked by NMR and x-ray analysis. At least two intermediate structures with distinct topologies were observed prior to the formation of the final double-walled cage. By optimizing the self-assembly conditions (e.g., time, solvent, and concentration), these topological intermediates were successfully isolated and analyzed by x-ray crystallography. They are considered crucial metastable structures that navigate the shortest pathway to the final structure, demonstrating the critical role of molecular topology in guiding and controlling the kinetics of metal-directed self-assembly.
通过核磁共振（NMR）和X射线分析追踪了由半柔性三脚架配体和钯（II）90度嵌段形成的双壁笼的自组装过程。在最终双壁笼形成之前，观察到至少两种具有不同拓扑结构的中间结构。通过优化自组装条件（例如时间、溶剂和浓度），这些拓扑中间体成功地被分离出来，并通过X射线晶体学进行了分析。它们被认为是至关重要的亚稳结构，引导着通往最终结构的最短路径，证明了分子拓扑在指导和控制金属导向自组装动力学方面的关键作用。
