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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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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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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Crystallographic data for compound 1·4PF6·2CH3CN (CIF 21 kb)
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Crystallographic data for compound 1·4PF6·CH3CN (CIF 32 kb)
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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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DOI: https://doi.org/10.1038/nchem.597
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