![]() Self-assembly of discrete cyclic nanostructures mediated by transition metals. Terpyridine-based metallosupramolecular constructs: tailored monomers to precise 2D-motifs and 3D-metallocages. Recent developments in the preparation and chemistry of metallacycles and metallacages via coordination. Supramolecular coordination: self-assembly of finite two- and three-dimensional ensembles. Tessellated multiporous two-dimensional covalent organic frameworks. Porous organic cages: soluble, modular and molecular pores. Interface-assisted synthesis of 2D materials: trend and challenges. Metal–organic frameworks as a tunable platform for designing functional molecular materials. Metal–organic frameworks for separations. ![]() Metal–organic framework materials as chemical sensors. Supramolecular polymers: historical development, preparation, characterization, and functions. Structures of metal–organic frameworks with rod secondary building units. Schoedel, A., Li, M., Li, D., O’Keeffe, M. Synthesis of metal-organic frameworks (MOFs): routes to various MOF topologies, morphologies, and composites. Two-dimensional soft nanomaterials: a fascinating world of materials. Electric field effect in atomically thin carbon films. Therefore, these systems could serve as ideal models for investigating the structure–property–function relationships of 2D materials. 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. 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. ![]() However, structures of intermediate size have not been widely explored because of challenges in their synthesis and characterization. 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. 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.
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