Thermodynamic and electrochemical study of tailor-made crown ethers for redox-switchable (pseudo)rotaxanes
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
Published inBeilstein Journal of Organic Chemistry
DisciplineOrgaaninen kemiaOrganic Chemistry
© 2020 Hupatz et al.; licensee Beilstein-Institut
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-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. ...
ISSN Search the Publication Forum1860-5397
Publication in research information system
MetadataShow full item record
Related funder(s)Academy of Finland
Funding program(s)Research costs of Academy Research Fellow, AoF
Additional information about fundingThis research was funded by the Deutsche Forschungsgemeinschaft and the Academy of Finland (decision no. 314343).
Showing items with similar title or keywords.
Chiroptical inversion of a planar chiral redox-switchable rotaxane Gaedke, Marius; Witte, Felix; Anhäuser, Jana; Hupatz, Henrik; Schröder, Hendrik V.; Valkonen, Arto; Rissanen, Kari; Lützen, Arne; Paulus, Beate; Schalley, Christoph A. (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 ...
Structure of SNX9 SH3 in complex with a viral ligand reveals the molecular basis of its unique specificity for alanine-containing class I SH3 motifs Tossavainen, Helena; Uğurlu, Hasan; Karjalainen, Mikael; Hellman, Maarit; Antenucci, Lina; Fagerlund, Riku; Saksela, Kalle; Permi, Perttu (Elsevier, 2022)Class I SH3 domain-binding motifs generally comply with the consensus sequence [R/K]xØPxxP, the hydrophobic residue Ø being proline or leucine. We have studied the unusual Ø = Ala-specificity of SNX9 SH3 by determining its ...
Ion pair recognition by ditopic crown ether based bis-urea and uranyl salophen receptors Mäkelä, Toni (University of Jyväskylä, 2016)
Strategies for Exploring Functions from Dynamic Combinatorial Libraries Jia, Chunman; Qi, Dawei; Zhang, Yucang; Rissanen, Kari; Li, Jianwei (Wiley-VCH Verlag, 2020)Dynamic combinatorial chemistry (DCC) is a powerful approach for creating complex chemical systems, giving access to the studies of complexity and exploration of functionality in synthetic systems. However, compared with ...
A supramolecular system that strictly follows the binding mechanism of conformational selection Yang, Liu-Pan; Zhang, Li; Quan, Mao; Ward, Jas S.; Ma, Yan-Long; Zhou, Hang; Rissanen, Kari; Jiang, Wei (Nature Publishing Group, 2020)Induced fit and conformational selection are two dominant binding mechanisms in biology. Although induced fit has been widely accepted by supramolecular chemists, conformational selection is rarely studied with synthetic ...