Although the principles of noncovalent bonding are well understood and form the basis for the syntheses of many intricate supramolecular structures, supramolecular noncovalent synthesis cannot yet achieve the levels of precision and complexity that are attainable in organic and/or macromolecular covalent synthesis. Here we show the stepwise synthesis of block supramolecular polymers from metal–porphyrin derivatives (in which the metal centre is Zn, Cu or Ni) functionalized with fluorinated alkyl chains. These monomers first undergo a one-dimensional supramolecular polymerization and cyclization process to form a toroidal structure. Subsequently, successive secondary nucleation, elongation and cyclization steps result in two-dimensional assemblies with concentric toroidal morphologies. The site selectivity endowed by the fluorinated chains, reminiscent of regioselectivity in covalent synthesis, enables the precise control of the compositions and sequences of the supramolecular structures, as demonstrated by the synthesis of several triblock supramolecular terpolymers.

尽管非共价键合的原理已被充分理解并构成了许多复杂超分子结构合成的基础，但超分子非共价合成尚未达到有机和/或大分子共价合成中可达到的精确度和复杂性水平。在这里，我们展示了由氟化烷基链功能化的金属卟啉衍生物（其中金属中心是锌、铜或镍）逐步合成嵌段超分子聚合物。这些单体首先经历一维超分子聚合和环化过程，形成环形结构。随后，连续的二次成核、伸长和环化步骤产生具有同心环形形态的二维组装体。氟化链赋予的位点选择性，