Article | Published:

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

Nature Chemistry volume 2, pages 893898 (2010) | Download Citation

Abstract

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.

  • Compound C12H14O4

    5-tert-Butyl-1,3-benzenedicarboxylic acid

  • Compound C8H6O5

    5-Hydroxy-1,3-benzenedicarboxylic acid

  • Compound C8H5NaO7S

    5-Sulfo-1,3-benzenedicarboxylic acid monosodium salt

  • Compound C16H10O4

    3,3’-(Ethyne-1,2-diyl)dibenzoic acid

  • Compound C12H8O4

    2,7-Naphthalenedicarboxylic acid

  • Compound C8H6O4

    1,3-Benzenedicarboxylic acid

  • Compound C27H21NO4

    3,3’-(2-Amino-5-iso-propyl-1,3-phenylene)bis(ethyne-2,1-diyl)dibenzoic acid

  • Compound C14H9NO4

    9H-3,6-Carbazoledicarboxylic acid

  • Compound C7H5NO4

    4-Nitrobenzenecarboxylic acid

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Acknowledgements

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

Affiliations

  1. Department of Chemistry, Texas A&M University, College Station, Texas 77842-3012, USA

    • Jian-Rong Li
    •  & Hong-Cai Zhou

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Contributions

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.

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DOI

https://doi.org/10.1038/nchem.803

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