Synthesis of electrochemically responsive TTF-based molecular tweezers: evidence of tight intramolecular TTF pairing in solution |
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Authors: | Vladimir A. Azov,Rafael Gó mez |
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Affiliation: | a University of Bremen, Department of Chemistry, Leobener Strasse NW 2C, D-28359 Bremen, Germany b Universidad Complutense, Departamento de Química Orgánica, Avda. Complutense s/n, E-28040 Madrid, Spain |
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Abstract: | We report the synthesis and conformational studies of TTF-containing molecular tweezers based on a 1,2,4,5-tetramethylbenzene scaffold. In the neutral form the tweezers are expected to adopt the closed conformation, while, upon oxidation, the open conformation should be preferred due to electrostatic repulsion between the oxidized TTF moieties. Cyclic voltammetry studies demonstrate electronic pairing with formation of mixed-valence [TTF]2+ species and opening of the tweezers upon the full oxidation of the TTF groups. Variable-temperature (VT) NMR studies evidence tight intramolecular TTF pairing at low temperature. Molecular modeling studies showed clear preference for an open conformation of tweezers in a fully oxidized state. |
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Keywords: | Molecular devices Conformational analysis NMR Cyclic voltammetry Tetrathiafulvalenes Stacking |
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