Increasing the size and complexity of discrete 2D metallosupramolecules

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. Large discrete 2D metallosupramolecules bridge the gap between small metallopolygons and infinite 2D metallopolymers, and are emerging platforms for the investigation of the structure-property-function relationships of 2D materials. This Review focuses on the design, synthesis and characterization of 2D metallosupramolecules, and presents a perspective on the future research directions.

Automated summary

This review focuses on the assembly of large 2D metallosupramolecular architectures through three distinct approaches, which combine the characteristics of macrocycles and infinite polymers, making them ideal models for investigating the structure-property-function relationships of 2D materials.