Journal article
Photochemical unmasking of polyyne rotaxanes
- Abstract:
- Bulky photolabile masked alkyne equivalents (MAEs) are needed for the synthesis of polyyne polyrotaxanes, as insulated molecular wires and as stabilized forms of the linear polymeric allotrope of carbon, carbyne. We have synthesized a novel MAE based on phenanthrene and compared it with an indane-based MAE. Photochemical unmasking of model compounds was studied at different wavelengths (250 and 350 nm), and key products were identified by NMR spectroscopy and X-ray crystallography. UV irradiation at 250 nm leads to unmasking of both MAEs. Irradiation of the phenanthrene system at 350 nm results in quantitative dimerization via [2 + 2] cycloaddition to form a [3]-ladderane; irradiation of this ladderane at 250 nm generates a dihydrotriphenylene, which can be oxidized easily to a triphenylene. Irradiation of the indane-based MAE at 350 nm in the presence of traces of oxygen forms an endoperoxide and a bisepoxide. Both MAEs have been incorporated into rotaxanes via copper-mediated active metal template Glaser or Cadiot–Chodkiewicz coupling. The identity of the rotaxanes was confirmed by NMR spectroscopy and mass spectrometry. The phenanthrene rotaxane decomposes during attempted photochemical unmasking, whereas photolysis of the indane rotaxane results in unmasking of the polyyne thread to form a rotaxane with a chain of 16 sp-hybridized carbon atoms. This approach opens avenues toward the synthesis of encapsulated carbon allotropes.
- Publication status:
- Published
- Peer review status:
- Peer reviewed
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- Files:
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(Preview, Supplementary materials, pdf, 11.3MB, Terms of use)
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(Preview, Accepted manuscript, pdf, 5.7MB, Terms of use)
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- Publisher copy:
- 10.1021/jacs.0c05308
Authors
- Publisher:
- American Chemical Society
- Journal:
- Journal of the American Chemical Society More from this journal
- Volume:
- 142
- Issue:
- 31
- Pages:
- 13523–13532
- Publication date:
- 2020-06-26
- Acceptance date:
- 2020-06-26
- DOI:
- EISSN:
-
1520-5126
- ISSN:
-
0002-7863
- Pmid:
-
32589030
- Language:
-
English
- Keywords:
- Subjects:
- Pubs id:
-
1116957
- Local pid:
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pubs:1116957
- Deposit date:
-
2020-07-08
- ARK identifier:
Terms of use
- Copyright holder:
- American Chemical Society
- Copyright date:
- 2020
- Rights statement:
- Copyright © 2020 American Chemical Society
- Notes:
- This is the accepted manuscript version of the article. The final version is available online from American Chemical Society at https://doi.org/10.1021/jacs.0c05308
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