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 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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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 (diazaCPP) and 2159306 (diazaCPP). 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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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.
The authors declare no competing interests.
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Experimental Details, NMR spectra of compounds, crystallographic information, computational details, Supplementary Figs. 1–72, discussion and Table 1.
.cif file for compound 1a.
.cif file for compound 1b..
.cif file for compound 2
.cif file for compound diazaCPP.
.cif file for compound diazaCPP.
.zip file containing 1H and 13 C NMR of all reported compounds.
.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. (2023). https://doi.org/10.1038/s41557-022-01106-9