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Issue 15, 2018
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An aryl-fused redox-active tetrathiafulvalene with enhanced mixed-valence and radical-cation dimer stabilities

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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.

Graphical abstract: An aryl-fused redox-active tetrathiafulvalene with enhanced mixed-valence and radical-cation dimer stabilities

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Publication details

The article was received on 16 Feb 2018, accepted on 21 Mar 2018 and first published on 21 Mar 2018


Article type: Paper
DOI: 10.1039/C8OB00415C
Citation: Org. Biomol. Chem., 2018,16, 2741-2747
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    An aryl-fused redox-active tetrathiafulvalene with enhanced mixed-valence and radical-cation dimer stabilities

    H. V. Schröder, F. Witte, M. Gaedke, S. Sobottka, L. Suntrup, H. Hupatz, A. Valkonen, B. Paulus, K. Rissanen, B. Sarkar and C. A. Schalley, Org. Biomol. Chem., 2018, 16, 2741
    DOI: 10.1039/C8OB00415C

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