Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan.
J Am Chem Soc. 2020 Sep 30;142(39):16661-16667. doi: 10.1021/jacs.0c06618. Epub 2020 Sep 16.
A two-ligand system composed of the predesigned multivalent and complementary terpyridine-based ligands was exploited to construct heteroleptic metallo-supramolecules and to investigate the self-assembly mechanism. Molecular stellation of the trimeric hexagon [Cd] gave rise to the exclusive self-assembly of the star hexagon [Cd] through complementary ligand pairing between the ditopic and octatopic tectons. To understand how the intermolecular heteroleptic complexation influenced the self-assembly pathway, the star hexagon was truncated into two triangular fragments: [Cd] and [Cd]. In the self-assembly of [Cd], the conformational movements of hexatopic ligand could be regulated by to promote the subsequent coordination event, which was the key step to the successful multicomponent self-assembly. In contrast, the formation of [Cd] was hampered by the geometrically mismatched intermediates.
采用由预先设计的多价和互补的三吡啶基配体组成的双配体体系，构建了杂金属超分子并研究了自组装机制。三聚体六边形[Cd]的分子星状化导致通过两个位置和八个位置结构单元之间的互补配体配对，仅通过星型六边形[Cd]的自组装来实现。为了理解分子间杂金属配合物如何影响自组装途径，将星型六边形截断为两个三角形片段：[Cd]和[Cd]。在[Cd]的自组装中，可以通过[Cd]调节六配位体的构象运动，以促进随后的配位事件，这是成功的多组分自组装的关键步骤。相比之下，[Cd]的形成受到了几何形状不匹配的中间体的阻碍。
