Bridging-ligand-substitution strategy for the preparation of metal–organic polyhedra


Metal–organic polyhedra—discrete molecular architectures constructed through the coordination of metal ions and organic linkers—have recently attracted considerable attention due to their intriguing structures, their potential for a variety of applications and their relevance to biological self-assembly. Several synthetic routes have been investigated to prepare these complexes. However, to date, these preparative methods have typically been based on the direct assembly of metal ions and organic linkers. Although these routes are convenient, it remains difficult to find suitable reaction conditions or to control the outcome of the assembly process. Here, we demonstrate a synthetic strategy based on the substitution of bridging ligands in soluble metal–organic polyhedra. The introduction of linkers with different properties from those of the initial metal–organic polyhedra can thus lead to new metal–organic polyhedra with distinct properties (including size and shape). Furthermore, partial substitution can also occur and form mixed-ligand species that may be difficult to access by means of other approaches.

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Figure 1: Structures of the building blocks.
Figure 2: Schematic of the syntheses and crystal structures of compounds 1–10.
Figure 3: Polyhedral representations of MOPs 4 and 5.
Figure 4: Polyhedral projection labelling of MOPs.
Figure 5: Gas adsorption isotherms of activated MOP 1.


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This material is based upon work supported as part of the Center for Gas Separations Relevant to Clean Energy Technologies, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under award no. DE-SC0001015. The authors thank A. Yakovenko for his help in crystal structure refinement and PXRD analysis.

Author information




J.R.L. and H.C.Z. conceived and designed the experiments, analysed data and co-wrote the paper. J.R.L. performed all experiments.

Corresponding author

Correspondence to Hong-Cai Zhou.

Supplementary information

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Supplementary information (PDF 1735 kb)

Supplementary information

nchem.803-S2.cif Crystallographic data for compound 1 (CIF 28 kb)

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nchem.803-S3.cif Crystallographic data for compound 2 (CIF 27 kb)

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nchem.803-S4.cif Crystallographic data for compound 3 (CIF 32 kb)

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nchem.803-S5.cif Crystallographic data for compound 4 (CIF 88 kb)

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nchem.803-S6.cif Crystallographic data for compound 5 (CIF 47 kb)

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nchem.803-S7.cif Crystallographic data for compound 6 (CIF 58 kb)

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nchem.803-S8.cif Crystallographic data for compound 7 (CIF 47 kb)

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nchem.803-S9.cif Crystallographic data for compound 8 (CIF 41 kb)

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nchem.803-S10.cif Crystallographic data for compound 9 (CIF 53 kb)

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nchem.803-S11.cif Crystallographic data for compound 10 (CIF 17 kb)

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Li, J., Zhou, H. Bridging-ligand-substitution strategy for the preparation of metal–organic polyhedra. Nature Chem 2, 893–898 (2010).

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