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Intra- and intermolecular self-assembly of a 20-nm-wide supramolecular hexagonal grid

An Author Correction to this article was published on 14 May 2020

This article has been updated


For the past three decades, the coordination-driven self-assembly of three-dimensional structures has undergone rapid progress; however, parallel efforts to create large discrete two-dimensional architectures—as opposed to polymers—have met with limited success. The synthesis of metallo-supramolecular systems with well-defined shapes and sizes in the range of 10–100 nm remains challenging. Here we report the construction of a series of giant supramolecular hexagonal grids, with diameters on the order of 20 nm and molecular weights greater than 65 kDa, through a combination of intra- and intermolecular metal-mediated self-assembly steps. The hexagonal intermediates and the resulting self-assembled grid architectures were imaged at submolecular resolution by scanning tunnelling microscopy. Characterization (including by scanning tunnelling spectroscopy) enabled the unambiguous atomic-scale determination of fourteen hexagonal grid isomers.

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Fig. 1: The synthetic strategy of ligand followed by intra- and intermolecular self-assembly of supramolecular hexagonal grids with Fe(ii).
Fig. 2: Mass spectrometry for characterization of the intra- and intermolecular self-assembly processes leading to 5.
Fig. 3: STM imaging of the intra- and intermolecular self-assembled structures on Ag (111) surface.
Fig. 4: Isomeric forms of 5 on substrate and their characterization by STS.

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All data supporting the findings of this study are available in the manuscript or the Supplementary Information.

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This research was supported by National Institutes of Health (grant no. R01GM128037 to X.L.). Use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. Support from Shanghai University is also gratefully acknowledged. T.R and A.T.N acknowledge the computing resources provided on Bebop, a high-performance computing cluster operated by the Laboratory Computing Resource Center at Argonne National Laboratory. This work was supported in part by the US Department of Energy, Office of Science, Office of Workforce Development for Teachers and Scientists (WDTS) under the Science Undergraduate Laboratory Internship (SULI) programme. We also acknowledge partial support through University of South Florida Nexus Initiative (UNI) Award and the Natural Science Foundation of Guangdong Province, China (grant no. 2019A1515011358 to Z.Z.).

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Authors and Affiliations



X.L. and Y.L. conceived and designed the experiments. Z.Z. and Y.L. completed the synthesis. Y.L., B.S., Y.Z., S. W. H and R.T performed STM. Z.Z., X.J. and M.W. conducted NMR. Z.Z. performed MS characterization. T.R. and A.T.N performed DFT calculations. Y.L., B.S., Z.Z., Y.Z., S.W.H, J.L.S., G.R.N. and X.L. analysed the data and wrote the manuscript. All the authors discussed the results and commented on and proofread the manuscript.

Corresponding authors

Correspondence to Yiming Li, Yuan Zhang, Jonathan L. Sessler, Saw Wai Hla or Xiaopeng Li.

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The authors declare no competing interests.

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Supplementary information

Supplementary Information

Structures of the species considered in this study; Synthesis and characterization data; computational data; Kondo resonance; Supplementary Schemes 1–6, Figs. 1–97 and references.

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Zhang, Z., Li, Y., Song, B. et al. Intra- and intermolecular self-assembly of a 20-nm-wide supramolecular hexagonal grid. Nat. Chem. 12, 468–474 (2020).

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