Chiroptical inversion of a planar chiral redox-switchable rotaxane
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
Published inChemical Science
© The Royal Society of Chemistry 2019
A tetrathiafulvalene (TTF)-containing crown ether macrocycle with Cs symmetry was designed to implement planar chirality into a redox-active rotaxane. The directionality of the macrocycle atom sequence together with the non-symmetric axle renders the corresponding rotaxane mechanically planar chiral. Enantiomeric separation of the 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.
PublisherRoyal Society of Chemistry
Publication in research information system
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Related funder(s)Academy of Finland
Funding program(s)Researcher mobility Funding, AoF; Research costs of Academy Research Fellow, AoF
Additional information about fundingWe thank the Deutsche Forschungsgemeinschaft (CRC 765) and Academy of Finland (KR proj. no. 309399, AV proj. no. 314343) for funding. We are grateful to the Alexander von Humboldt-Foundation for support of KR (AvH research award). JA thanks the Studienstiftung des deutschen Volkes for a doctoral scholarship.
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