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Increasing the size and complexity of discrete 2D metallosupramolecules

Nature Reviews Materials volume 6, pages 145–167 (2021)Cite this article

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Abstract

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.

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Fig. 1: Development of three types of discrete 2D metallosupramolecules.
Fig. 2: Supramolecular polygons with metals at the edges.
Fig. 3: Supramolecular polygons directed by organic templates and polygrams with metals at the corners.
Fig. 4: Supramolecular concentric polygons with rigid organic spokes.
Fig. 5: Supramolecular concentric polygons with flexible organic spokes or coordination spokes.
Fig. 6: Supramolecular triangular tessellations without a hexatopic core ligand.
Fig. 7: Supramolecular triangular tessellations with a hexatopic core ligand.
Fig. 8: Supramolecular hexagonal tessellations.
Fig. 9: Supramolecular square tessellations.
Fig. 10: Characterization of 2D metallosupramolecules with mass spectrometry.
Fig. 11: Characterization of 2D metallosupramolecules with AFM and STM.

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Acknowledgements

The authors acknowledge support from Shenzhen University, the University of South Florida and Texas State University. X.L. acknowledges the Tencent Founders Alumni (TFA) Foundation for support.

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Authors and Affiliations

  1. Shenzhen University General Hospital, Shenzhen University Clinical Medical Academy, Shenzhen, China

    Heng Wang & Xiaopeng Li

  2. College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, China

    Heng Wang, Yiming Li & Xiaopeng Li

  3. Department of Chemistry, University of South Florida, Tampa, FL, USA

    Yiming Li & Alexander Filosa

  4. Faculty of Education and Sports, Guangdong Baiyun University, Guangzhou, China

    Na Li

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  1. Heng Wang
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All authors contributed to the discussion of content and the editing of the manuscript prior to submission. H.W., N.L. and X.L. researched the data. H.W., N.L. and X.L. wrote the manuscript, with help from Y.L. and A.F.

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Wang, H., Li, Y., Li, N. et al. Increasing the size and complexity of discrete 2D metallosupramolecules. Nat Rev Mater 6, 145–167 (2021). https://doi.org/10.1038/s41578-020-00257-w

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