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Photochemical unmasking of polyyne rotaxanes

DOI: 10.1021/jacs.0c05308 DOI Help

Authors: Steffen Woltering (University of Oxford) , Przemyslaw Gawel (University of Oxford) , Kirsten E. Christensen (University of Oxford) , Amber L. Thompson (University of Oxford) , Harry L. Anderson (University of Oxford)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society

State: Published (Approved)
Published: June 2020
Diamond Proposal Number(s): 20876

Abstract: Bulky photo-labile 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 nm 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 towards the synthesis of encapsulated carbon allotropes.

Journal Keywords: Hydrocarbons; Rotaxanes; Aromatic compounds; Macrocycles; Irradiation

Subject Areas: Chemistry

Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 29/06/2020 09:29

Discipline Tags:

Chemistry Organic Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)