Department of Chemistry and Biochemistry, Texas State University , San Marcos, Texas 78666, United States.
J Am Chem Soc. 2014 Jul 23;136(29):10499-507. doi: 10.1021/ja505414x. Epub 2014 Jul 9.
Using a series of tritopic 2,2':6',2″-terpyridine (tpy) ligands constructed on adamantane, three discrete 3D metallo-supramolecular architectures were assembled, i.e., trigonal bipyramidal, tetrahedron, and cube. The self-assembly used tritopic ligands as corner directing units and metal ions as glue units at the edge. The angles of the linkers between adamantane and tpy head play a critical role in guiding the assembled structures, which have the general formula of M3nL2n, where M denotes metal ion and L denotes ligand. All complexes were fully characterized by (1)H, (13)C NMR, diffusion-ordered NMR spectroscopy, ESI-MS, and traveling-wave ion mobility-mass spectrometry. The binary mixtures of LA and LC or LB and LC underwent a self-sorting process that led to the self-assembly of discrete 3D structures. The self-sorting behavior is solely based on the angles precoded within the arm of tritopic ligands. Moreover, kinetic study of preassembled cube and tetrahedron demonstrated a slow ligand exchange process toward a statistical mixture of hetero tetrahedrons with LA and LB.
使用一系列基于金刚烷构建的三齿 2,2':6',2″-三联吡啶 (tpy) 配体，组装了三种离散的 3D 金属超分子架构，即三角双锥、四面体和立方体。自组装使用三齿配体作为角导向单元，金属离子作为边缘的胶单元。金刚烷和 tpy 头之间的连接体的角度在引导组装结构方面起着关键作用，其通式为 M3nL2n，其中 M 表示金属离子，L 表示配体。所有配合物均通过 (1)H、(13)C NMR、扩散有序 NMR 光谱、ESI-MS 和行波离子迁移质谱进行了充分表征。LA 和 LC 或 LB 和 LC 的二元混合物经历了自分类过程，导致离散 3D 结构的自组装。自分类行为仅基于三齿配体臂内预先编码的角度。此外，预组装立方体和四面体的动力学研究表明，配体交换过程缓慢，朝着具有 LA 和 LB 的异四面体的统计混合物进行。
