A1 Journal article (refereed)
Chiroptical inversion of a planar chiral redox-switchable rotaxane (2019)

Gaedke, M., Witte, F., Anhäuser, J., Hupatz, H., Schröder, H. V., Valkonen, A., Rissanen, K., Lützen, A., Paulus, B., & Schalley, C. A. (2019). Chiroptical inversion of a planar chiral redox-switchable rotaxane. Chemical Science, 10(43), 10003-10009. https://doi.org/10.1039/C9SC03694F

JYU authors or editors

Publication details

All authors or editors: Gaedke, Marius; Witte, Felix; Anhäuser, Jana; Hupatz, Henrik; Schröder, Hendrik V.; Valkonen, Arto; Rissanen, Kari; Lützen, Arne; Paulus, Beate; Schalley, Christoph A.

Journal or series: Chemical Science

ISSN: 2041-6520

eISSN: 2041-6539

Publication year: 2019

Volume: 10

Issue number: 43

Pages range: 10003-10009

Publisher: Royal Society of Chemistry

Publication country: United Kingdom

Publication language: English

DOI: https://doi.org/10.1039/C9SC03694F

Publication open access: Openly available

Publication channel open access: Open Access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/67080

Abstract

A tetrathiafulvalene (TTF)-containing crown ether macrocycle with Cs 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.

Keywords: macromolecules

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Ministry reporting: Yes

Reporting Year: 2019

JUFO rating: 3