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A pentagonal cyanostar macrocycle with cyanostilbene CH donors binds anions and forms dialkylphosphate [3]rotaxanes

Nature Chemistry volume 5, pages 704–710 (2013)Cite this article

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Abstract

Since the discovery of crown ethers, macrocycles have been recognized as powerful platforms for supramolecular chemistry. Although their numbers and variations are now legion, macrocycles that are simple to make using high-yielding reactions in one pot and on the multigram scale are rare. Here we present such a discovery obtained during the creation of a C5-symmetric cyanostilbene ‘campestarene’ macrocycle, cyanostar, that employs Knoevenagel condensations in the preparation of its cyanostilbene repeat unit. In the solid state, cyanostars form π-stacked dimers constituted of chiral P and M enantiomers. The electropositive central cavity stabilizes anions with CH hydrogen-bonding units that are activated by electron-withdrawing cyano groups. In solution, the cyanostar shows high-affinity binding as 2:1 sandwich complexes, log β2 ≈ 12 and ΔG ≈ −70 kJ mol−1, of large anions (BF4−, ClO4− and PF6−) usually considered weakly coordinating. The cyanostar's size preference allowed formation of an unprecedented [3]rotaxane templated around a dialkylphosphate.

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Figure 1: Cyanostar (CS), a cyanostilbene-based macrocycle with five-fold symmetry.
Figure 2: Stereoisomers and WMD in the crystal structure.
Figure 3: Anion binding selectivity of cyanostars.
Figure 4: NMR spectroscopic characterization of anion complexes.
Figure 5: Formation and characterization of phosphate-templated [3]rotaxanes.

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Acknowledgements

We acknowledge the National Science Foundation (NSF/CHE-0844441) for financial support. S.L. thanks the Raymond Siedle Fellowship in Materials Chemistry. Crystal data were recorded using ChemMatCARS Sector 15, principally supported by the NSF and Department of Energy under grant number NSF/CHE-0822838. Use of the Advanced Photon Source was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.

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  1. Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, 47405, Indiana, USA

    Semin Lee, Chun-Hsing Chen & Amar H. Flood

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Contributions

S.L. conceived this project, and designed and conducted the syntheses and experiments. C-H.C. conducted the crystallographic study. S.L. and A.H.F. contributed to the data analysis and co-wrote the paper.

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Correspondence to Amar H. Flood.

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Crystallographic data for compound CS. (CIF 73 kb)

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Crystallographic data for compound 3TBA. (CIF 161 kb)

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Lee, S., Chen, CH. & Flood, A. A pentagonal cyanostar macrocycle with cyanostilbene CH donors binds anions and forms dialkylphosphate [3]rotaxanes. Nature Chem 5, 704–710 (2013). https://doi.org/10.1038/nchem.1668

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