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Quantitative self-assembly of a purely organic three-dimensional catenane in water

Nature Chemistry volume 7, pages 1003–1008 (2015)Cite this article

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Abstract

Self-assembly by means of coordinative bond formation has opened up opportunities for the high-yield synthesis of molecules with complex topologies. However, the preparation of purely covalent molecular architectures in aqueous media has remained a challenging task. Here, we present the preparation of a three-dimensional catenane through a self-assembly process that relies on the formation of dynamic hydrazone linkages in an acidic aqueous medium. The quantitative synthesis process and the mechanically interlocked structure of the resulting catenane were established by NMR spectroscopy, mass spectrometry, X-ray crystallography and HPLC studies. In addition, the labile hydrazone linkages of the individual [2]catenane components may be ‘locked’ by increasing the pH of the solution, yielding a relatively kinetically stable molecule. The present study thus details a simple approach to the creation and control of complex molecular architectures under reaction conditions that mimic biological milieux.

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Figure 1: Structural formulae of precursors A13+, H1 and the [2]catenane C6+.
Figure 2: Partial 1H NMR spectra (400 MHz, D2O, 298 K) of the [2]catenane C6+ and the corresponding starting materials A13+·3Cl– and H1.
Figure 3: Side view of the core structure of C6+ obtained from single-crystal X-ray diffraction analysis of C6+·6Cl−.
Figure 4: ESI-MS of [2]catenane C6+·6CF3CO2−.
Figure 5: Reversed-phase HPLC analysis of the [2]catenane formation reaction in acidic water.
Figure 6: ESI-MS analyses of aqueous solutions of [2]catenane C6+ containing different quantities of DMSO.

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Acknowledgements

This work was supported by the US National Science Foundation (grant no. CHE-1402004) and the Robert A. Welch Foundation (F-1018). H.L. acknowledges support from a Chinese Government Award under the ‘Outstanding Self-Financed Student Abroad and the Thousand Young Talents Plan’. X.L. acknowledges support from the National Science Foundation (CHE-1506722) and the PREM Center for Interfaces (DMR-1205670).

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Authors and Affiliations

  1. Department of Chemistry, Zhejiang University, Hangzhou, 310027, China

    Hao Li

  2. Department of Chemistry, The University of Texas at Austin, Austin, 78712, Texas, USA

    Hao Li, Huacheng Zhang, Aaron D. Lammer, Vincent M. Lynch & Jonathan L. Sessler

  3. Department of Chemistry and Biochemistry & Materials Science, Engineering, and Commercialization Program, Texas State University, San Macros, 78666, Texas, USA

    Ming Wang & Xiaopeng Li

  4. Department of Chemistry, Innovative Drug Research Center, and School of Materials Science and Engineering, Shanghai University, Shanghai, 200444, China

    Jonathan L. Sessler

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  1. Hao Li
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Contributions

H.L. and J.L.S. conceived the project. H.L. and J.L.S. prepared the manuscript. H.L., H.Z. and A.D.L. synthesized the molecules studied in this work. V.M.L. solved the crystal structure. H.L., M.W. and X.L. were responsible for MS studies. H.L. performed the NMR spectroscopic and HPLC investigations.

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Correspondence to Hao Li or Jonathan L. Sessler.

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Crystallographic data for compound C6+.6Cl- (CIF 2075 kb)

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Li, H., Zhang, H., Lammer, A. et al. Quantitative self-assembly of a purely organic three-dimensional catenane in water. Nature Chem 7, 1003–1008 (2015). https://doi.org/10.1038/nchem.2392

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