Owing to the reversible, directional and predictable nature of metal–ligand coordination, coordination-driven self-assembly has emerged as a powerful bottom-up strategy for preparing metal-containing supramolecules or materials. In the field of 2D constructs, considerable progress has been made in the coordination-driven self-assembly of small discrete polygons (<5 nm) and infinite 2D polymers. However, structures of intermediate size have not been widely explored because of challenges in their synthesis and characterization. In this Review, we focus on the assembly of large 2D metallosupramolecular architectures of increasing size and complexity through three distinct approaches: expanding the size of macrocycles, increasing the number of layers within concentric polygons and forming complex structures by tessellation. These large but discrete 2D metallosupramolecules possess the unique features of both macrocycles, including a precisely controlled structure with high solubility for solution-based applications and characterization, and infinite polymers, such as an ordered distribution of the functionalities. Therefore, these systems could serve as ideal models for investigating the structure–property–function relationships of 2D materials.

由于金属-配体配位的可逆性，方向性和可预测性，配位驱动的自组装已成为制备含金属超分子或材料的强大的自下而上策略。在2D构造领域，小离散多边形（<5 nm）和无限2D聚合物的协调驱动自组装已取得了相当大的进步。然而，由于其合成和表征方面的挑战，中等尺寸的结构尚未得到广泛研究。在这篇综述中，我们着重于通过三种不同的方法来组装大型2D金属超分子体系结构，这些体系结构具有越来越大的尺寸和复杂性：扩展大环的尺寸，增加同心多边形内的层数以及通过镶嵌来形成复杂的结构。这些大而离散的二维金属超分子具有两个大环的独特特征，包括对溶液的应用和表征具有高溶解度的精确控制的结构，以及无限大的聚合物，例如功能的有序分布。因此，这些系统可以作为研究2D材料的结构-性能-功能关系的理想模型。