Takudrei

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Impact of mechanical bonding on the redox-switching of tetrathiafulvalene in crown ether-ammonium [2]rotaxanes

H.V. Schröder, S. Sobottka, M. Nößler, H. Hupatz, M. Gaedke, B. Sarkar, C.A. Schalley— 2017

Switchable crown ether–ammonium [2]rotaxanes with a redox-active tetrathiafulvalene (TTF) unit implemented in their wheels were synthesised and fully characterised. Reversible operation in two modes is possible, in which the [2]rotaxane's axle is either charged or neutral. Cyclic voltammetry experiments reveal the effects of mechanical bonding on the electrochemical properties of TTF and show the [2]rotaxanes to perform a distinct function in both modes. In the charged mode, redox- switching is dominated by strong electrostatic repulsion in the [2]rotaxane which subsequently leads to a macrocycle translation along the axle. In the non-charged mode, a selective energetic stabilisation of TTF radical cations is observed, which can be attributed to an interplay of weak electrostatic interactions between wheel and axle.

Title232
Impact of mechanical bonding on the redox-switching of tetrathiafulvalene in crown ether-ammonium [2]rotaxanes
AuthorH.V. Schröder, S. Sobottka, M. Nößler, H. Hupatz, M. Gaedke, B. Sarkar, C.A. Schalley
Date20170710
IdentifierDOI: 10.1039/c7sc02694c
Source(s)
CitationChem. Sci. 2017, 8, 6300-6306
TypeText