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A ‘Texas-sized’ molecular box that forms an anion-induced supramolecular necklace

Nature Chemistry volume 2, pages 406–409 (2010)Cite this article

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Abstract

The ‘blue box’ (cyclobis(paraquat-p-phenylene) or CBPQT4+), developed by Stoddart and colleagues, forms effective charge transfer complexes with a variety of electron-rich species and has been used to support the formation of a wide range of interlocked structures. However, little effort seems to have been devoted to generalizing the blue box concept. We describe a new flexible tetracationic macrocycle—a ‘Texas-sized’ molecular box. This positively charged receptor is capable of binding the mono-terephthalate anion, forming pseudorotaxanes. These pseudorotaxanes self-assemble into short supramolecular pseudo-oligorotaxanes in solution and more extended pseudo-polyrotaxanes in the solid state. The supramolecular oligomers formed in solution are environmentally responsive; they undergo deaggregation as the overall concentration of the cationic and anionic constituents is reduced, the temperature is increased, or the protonation state of the threading mono-terephthalate anion is changed.

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Figure 1: Synthesis of the tetracationic imidazolium macrocycle 14+.
Figure 2: Two crystallographically independent single-crystal X-ray structures of 14+·4PF6−.
Figure 3: Observed binding interactions between host 14+ and terephthalic acid, mono-terephthalate anion and di-terephthalate anion.
Figure 4: Single X-ray crystal structure of [14+·mono-terephthalate·3PF6·4H2O].

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Acknowledgements

The authors are grateful to the National Science Foundation (grant no. CHE 0749571 to J.L.S. and grant no. 0741973 for the X-ray diffractometer) and the Robert A. Welch Foundation (grant F-1018 to J.L.S.) for financial support. Thanks also go to S. Sorey, C. Bielawski, A. Tennyson and K. Keller for their assistance with the NMR spectral, VPO and mass spectrometric studies.

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Authors and Affiliations

  1. Department of Chemistry & Biochemistry, 1 University Station A5300, The University of Texas at Austin, Austin, 78712-0165, Texas, USA

    Han-Yuan Gong, Brett M. Rambo, Elizabeth Karnas, Vincent M. Lynch & Jonathan L. Sessler

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  1. Han-Yuan Gong
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Contributions

J.L.S. and H.-Y.G. conceived this project and designed the experiments. H.-Y.G. contributed to the experimental work. V.M.L. contributed to the crystallographic study. H.-Y.G., B.M.R and E.K. contributed to the data analysis. H.-Y.G., B.M.R., E.K. and J.L.S. co-wrote the paper.

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Correspondence to Jonathan L. Sessler.

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The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 2976 kb)

Supplementary information

Crystallographic data for compound 1·4PF6·2CH3CN (CIF 21 kb)

Supplementary information

Crystallographic data for compound 1·4PF6·CH3CN (CIF 32 kb)

Supplementary information

Crystallographic data for compound 1·mono-terephthalate anion·3PF6·4H2O (CIF 22 kb)

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Gong, HY., Rambo, B., Karnas, E. et al. A ‘Texas-sized’ molecular box that forms an anion-induced supramolecular necklace. Nature Chem 2, 406–409 (2010). https://doi.org/10.1038/nchem.597

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