A1 Journal article (refereed)
Thermodynamic and electrochemical study of tailor-made crown ethers for redox-switchable (pseudo)rotaxanes (2020)

Hupatz, H., Gaedke, M., Schröder, H., Beerhues, J., Valkonen, A., Klautzsch, F., Müller, S., Witte, F., Rissanen, K., Sarkar, B., & Schalley, C. A. (2020). Thermodynamic and electrochemical study of tailor-made crown ethers for redox-switchable (pseudo)rotaxanes. Beilstein Journal of Organic Chemistry, 16, 2576-2588. https://doi.org/10.3762/bjoc.16.209

JYU authors or editors

Publication details

All authors or editors: Hupatz, Henrik; Gaedke, Marius; Schröder, Hendrik, V.; Beerhues, Julia; Valkonen, Arto; Klautzsch, Fabian; Müller, Sebastian; Witte, Felix; Rissanen, Kari; Sarkar, Biprajit; et al.

Journal or series: Beilstein Journal of Organic Chemistry

ISSN: 1860-5397

eISSN: 1860-5397

Publication year: 2020

Volume: 16

Pages range: 2576-2588

Publisher: Beilstein Institut

Publication country: Germany

Publication language: English

DOI: https://doi.org/10.3762/bjoc.16.209

Publication open access: Openly available

Publication channel open access: Open Access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/72284

Abstract

Crown ethers are common building blocks in supramolecular chemistry and are frequently applied as cation sensors or as subunits in synthetic molecular machines. Developing switchable and specifically designed crown ethers enables the implementation of function into molecular assemblies. Seven tailor-made redox-active crown ethers incorporating tetrathiafulvalene (TTF) or naphthalene diimide (NDI) as redox-switchable building blocks are described with regard to their potential to form redox-switchable rotaxanes. A combination of isothermal titration calorimetry and voltammetric techniques reveals correlations between the binding energies and redox-switching properties of the corresponding pseudorotaxanes with secondary ammonium ions. For two different weakly coordinating anions, a surprising relation between the enthalpic and entropic binding contributions of the pseudorotaxanes was discovered. These findings were applied to the synthesis of an NDI-[2]rotaxane, which retains similar spectroelectrochemical properties compared to the corresponding free macrocycle. The detailed understanding of the thermodynamic and electrochemical properties of the tailor-made crown ethers lays the foundation for the construction of new types of molecular redox switches with emergent properties.

Keywords: supramolecular chemistry

Free keywords: crown ether; isothermal titration calorimetry; redox chemistry; rotaxanes; supramolecular chemistry

Contributing organizations

Related projects

Ministry reporting: Yes

Reporting Year: 2020

JUFO rating: 1