Coordination-driven self-assembly is a powerful approach for the construction of metallosupramolecules, but designing coordination moieties that can drive the self-assembly with high selectivity and specificity remains a challenge. Here we report two ortho-modified terpyridine ligands that form head-to-tail coordination complexes with Zn(II). Both complexes show narcissistic self-sorting behaviour. In addition, starting from these ligands, we obtain two sterically congested multitopic ligands and use them to construct more complex metallo-supramolecules hexagons. Because of the non-coaxial structural restrictions in the rotation of terpyridine moieties, these hexagonal macrocycles can hierarchically self-assemble into giant cyclic nanostructures via edge-to-edge stacking, rather than face-to-face stacking. Our design of dissymmetrical coordination moieties from congested coordination pairs show remarkable self-assembly selectivity and specificity.

配位驱动的自组装是构建金属超分子的有效方法，但设计能够以高选择性和特异性驱动自组装的配位部分仍然是一个挑战。在这里，我们报告了两个与 Zn(II) 形成头尾配位配合物的邻位修饰三联吡啶配体。两种情结都表现出自恋的自我分类行为。此外，从这些配体开始，我们获得了两个空间拥挤的多主题配体，并用它们构建更复杂的金属超分子六边形。由于三联吡啶部分旋转的非同轴结构限制，这些六边形大环可以通过边到边堆叠而不是面对面堆叠来分层自组装成巨大的环状纳米结构。