A1 Journal article (refereed)
An aryl-fused redox-active tetrathiafulvalene with enhanced mixed-valence and radical-cation dimer stabilities (2018)
Schröder, H. V., Witte, F., Gaedke, M., Sobottka, S., Suntrup, L., Hupatz, H., Valkonen, A., Paulus, B., Rissanen, K., Sarkar, B., & Schalley, C. A. (2018). An aryl-fused redox-active tetrathiafulvalene with enhanced mixed-valence and radical-cation dimer stabilities. Organic and Biomolecular Chemistry, 16(15), 2741-2747. https://doi.org/10.1039/C8OB00415C
JYU authors or editors
Publication details
All authors or editors: Schröder, Hendrik V.; Witte, Felix; Gaedke, Marius; Sobottka, Sebastian; Suntrup, Lisa; Hupatz, Henrik; Valkonen, Arto; Paulus, Beate; Rissanen, Kari; Sarkar, Biprajit; et al.
Journal or series: Organic and Biomolecular Chemistry
ISSN: 1477-0520
eISSN: 1477-0539
Publication year: 2018
Volume: 16
Issue number: 15
Pages range: 2741-2747
Publisher: Royal Society of Chemistry
Publication country: United Kingdom
Publication language: English
DOI: https://doi.org/10.1039/C8OB00415C
Publication open access: Not open
Publication channel open access:
Abstract
Molecular recognition of stable organic radicals is a relatively novel, but important structural binding motif in supramolecular chemistry. Here, we report on a redox-switchable veratrole-fused tetrathiafulvalene derivative VTTF which is ideally suited for this purpose and for the incorporation into stimuli-responsive systems. As revealed by electrochemistry, UV/Vis measurements, X-ray analysis, and electrocrystallisation, VTTF can be reversibly oxidised to the corresponding radical-cation or dication which shows optoelectronic and structural propterties similar to tetrathiafulvalene and tetrakis(methylthio)tetrathiafulvalene. However, theoretical calculations, variable temperature EPR, and NIR spectroscopy indicate that the dispersion-driven binding in the mixed-valence dimer (VTTF2)˙+ (KMV = 69 M−1 in CH2Cl2) and the radical-cation dimer (VTTF˙+)2 (KRC = 38 M−1 in CH3CN) is significantly enhanced by the additional veratrole π-surface in comparison to pristine tetrathiafulvalene.
Keywords: supramolecular chemistry
Contributing organizations
Related projects
- Weak Interactions as Structural Elements in Self-assembling Molecular Systems
- Rissanen, Kari
- Research Council of Finland
- Robust S...I+...S Halogen Bonded Supramolecular Assemblies (research costs)
- Valkonen, Arto
- Research Council of Finland
Ministry reporting: Yes
Reporting Year: 2018
JUFO rating: 1