Komine Shohei, Takahashi Satoshi, Kojima Tatsuo, Sato Hirofumi, Hiraoka Shuichi
Department of Basic Science, Graduate School of Arts and Sciences , The University of Tokyo , 3-8-1 Komaba , Meguro-ku , Tokyo 153-8902 , Japan.
Department of Molecular Engineering , Kyoto University , Kyoto 615-8510 , Japan.
J Am Chem Soc. 2019 Feb 20;141(7):3178-3186. doi: 10.1021/jacs.8b12890. Epub 2019 Feb 11.
The self-assembly processes of two kinds of octahedron-shaped ML cages consisting of cis-protected Pd(II) complexes and organic tritopic ligands were investigated. Whether kinetically trapped species larger than the cages are produced or the ML cage is assembled without the formation of such kinetic traps is determined by a balance between the rates of oligomerization and intramolecular cyclization, which is affected by slight changes in the chemical structure of the tritopic ligand. A numerical analysis of the experimental data based on a reaction network model where 249 reactions between the possible 56 species were considered revealed the self-assembly pathways of one of the two ML cages.
研究了由顺式保护的钯（II）配合物和有机三齿配体组成的两种八面体形状的金属-配体（ML）笼的自组装过程。大于笼状结构的动力学捕获物种是否会产生，或者ML笼是否在不形成此类动力学陷阱的情况下组装，取决于低聚反应速率和分子内环化反应速率之间的平衡，而这又受到三齿配体化学结构微小变化的影响。基于一个反应网络模型对实验数据进行数值分析，该模型考虑了56种可能物种之间的249个反应，揭示了两种ML笼之一的自组装途径。
