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Active template strategy for the preparation of π-conjugated interlocked nanocarbons

Nature Chemistry volume 15, pages 170–176 (2023)Cite this article

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Abstract

Mechanically interlocked carbon nanostructures represent a relatively unexplored frontier in carbon nanoscience due to the difficulty in preparing these unusual topological materials. Here we illustrate an active-template method in which a [n]cycloparaphenylene precursor macrocycle is decorated with two convergent pyridine donors that coordinate to a metal ion. The metal ion catalyses alkyne–alkyne cross-coupling reactions within the central cavity of the macrocycle, and the resultant interlocked products can be converted into fully π-conjugated structures in subsequent synthetic steps. Specifically, we report the synthesis of a family of catenanes that comprise two or three mutually interpenetrating [n]cycloparaphenylene-derived macrocycles of various sizes. Additionally, a fully π-conjugated [3]rotaxane was synthesized by the same method. The development of synthetic methods to access mechanically interlocked carbon nanostructures of varying topology can help elucidate the implications of mechanical bonding for this emerging class of nanomaterials and allow structure–property relationships to be established.

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Fig. 1: Methods to synthesize π-conjugated interlocked nanocarbon species.
Fig. 2: Preparation of π-conjugated catenanes.
Fig. 3: X-ray structures of 1a, 1b and 2.
Fig. 4: Synthesis of a fully π-conjugated [3]rotaxane.
Fig. 5: Photophysical characteristics of compounds.
Fig. 6: Effect of N-atom positioning on the AT reaction.

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Data availability

Experimental procedures for the synthesis of all the compounds are available in the Supplementary Information. Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2159304 (1a), 2159303 (1b), 2159302 (2), 2159305 (diaza[8]CPP) and 2159306 (diaza[9]CPP). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. In addition to the spectra provided in the Supplementary Information, raw 1H and 13C data for all the novel structures are provided as Supplementary Data 6.

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Acknowledgements

This project was supported by the National Science Foundation (CHE-1808791). J.H.M. and R.L.M. were additionally supported by National Science Foundation Graduate Research Fellowships.

Author information

Authors and Affiliations

  1. Department of Chemistry and Biochemistry, Materials Science Institute, and Knight Campus for Accelerating Scientific Impact, University of Oregon, Oregon, USA

    James H. May, Jeff M. Van Raden, Ruth L. Maust & Ramesh Jasti

  2. CAMCOR—Center for Advanced Materials Characterization in Oregon, University of Oregon, Oregon, USA

    Lev N. Zakharov

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  1. James H. May
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Contributions

J.H.M., J.M.V.R. and R.J. were responsible for the conceptualization of the project. All the synthetic steps reported were performed by J.H.M. along with the computational and photophysical analyses. J.H.M. and R.J. drafted the original version of the manuscript with editing from J.M.V.R. and R.L.M. L.N.Z. collected and analysed all the crystallographic data.

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Correspondence to Ramesh Jasti.

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Competing interests

The authors declare no competing interests.

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Peer review information

Nature Chemistry thanks Birgit Esser and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Experimental Details, NMR spectra of compounds, crystallographic information, computational details, Supplementary Figs. 1–72, discussion and Table 1.

Supplementary Data 1

.cif file for compound 1a.

Supplementary Data 2

.cif file for compound 1b..

Supplementary Data 3

.cif file for compound 2

Supplementary Data 4

.cif file for compound diaza[8]CPP.

Supplementary Data 5

.cif file for compound diaza[9]CPP.

Supplementary Data 6

.zip file containing 1H and 13 C NMR of all reported compounds.

Supplementary Data 7

.out file for the optimized structures of [11 + 2]CPP and [12 + 4]CPP.

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May, J.H., Van Raden, J.M., Maust, R.L. et al. Active template strategy for the preparation of π-conjugated interlocked nanocarbons. Nat. Chem. 15, 170–176 (2023). https://doi.org/10.1038/s41557-022-01106-9

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