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      Chiroptical inversion of a planar chiral redox-switchable rotaxane†

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          Abstract

          Reversible redox-switching of a planar chiral [2]rotaxane with a tetrathiafulvalene-bearing crown ether macrocycle generates a complete sign reversal of the main band in the ECD spectrum, as shown by experiment and rationalised by DFT calculations.

          Abstract

          A tetrathiafulvalene (TTF)-containing crown ether macrocycle with C s symmetry was designed to implement planar chirality into a redox-active [2]rotaxane. The directionality of the macrocycle atom sequence together with the non-symmetric axle renders the corresponding [2]rotaxane mechanically planar chiral. Enantiomeric separation of the [2]rotaxane was achieved by chiral HPLC. The electrochemical properties – caused by the reversible oxidation of the TTF – are similar to a non-chiral control. Reversible inversion of the main band in the ECD spectra for the individual enantiomers was observed after oxidation. Experimental evidence, conformational analysis and DFT calculations of the neutral and doubly oxidised species indicate that mainly electronic effects of the oxidation are responsible for the chiroptical switching. This is the first electrochemically switchable rotaxane with a reversible inversion of the main ECD band.

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          Author and article information

          Journal
          Chem Sci
          Chem Sci
          Chemical Science
          Royal Society of Chemistry
          2041-6520
          2041-6539
          4 September 2019
          21 November 2019
          4 September 2019
          : 10
          : 43
          : 10003-10009
          Affiliations
          [a ] Institut für Chemie und Biochemie , Freie Universität Berlin , Takustr. 3 , 14195 Berlin , Germany . Email: c.schalley@ 123456schalley-lab.de
          [b ] Kekulé-Institut für Organische Chemie und Biochemie , Universität Bonn , Gerhard-Domagk-Str. 1 , 53121 Bonn , Germany
          [c ] University of Jyvaskyla , Department of Chemistry , P.O. Box 35 , 40014 Jyväskylä , Finland
          Author information
          http://orcid.org/0000-0002-6126-0055
          http://orcid.org/0000-0003-2806-3807
          http://orcid.org/0000-0002-7282-8419
          http://orcid.org/0000-0003-4429-0823
          http://orcid.org/0000-0002-8634-3578
          Article
          c9sc03694f
          10.1039/c9sc03694f
          7003955
          32055357
          a3b07a1a-4046-4d0f-8163-1e6ba26e78d0
          This journal is © The Royal Society of Chemistry 2019

          This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0)

          History
          : 26 July 2019
          : 4 September 2019
          Categories
          Chemistry

          Notes

          †Electronic supplementary information (ESI) available: Synthetic procedures including full characterisation of new compounds, electrochemical data, crystallographic data and mass spectrometry data. CCDC 1910670. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c9sc03694f


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