Synthesis and electrochemistry of new tetrathiafulvalene (TTF) dendrimers:X-ray crystal structure of a tetrafunctionalised TTF core unit

Abstract
A new synthetic approach to tetrathiafulvalene (TTF) dendrimers is reported. Tetrakis(4-chloromethylbenzylthio)tetrathiafulvalene7 is a functionalised core unit which reacts with four equivalents of the thiolate ion generated from compound 16 to afford the trisdeca-TTF derivative 3. Compound 3 is a shelf-stable solid which has been characterised by elemental analysis, MALDI-TOF mass spectrometry, 1 H NMR spectroscopy and solution electrochemistry. Thin layer cyclic voltammetry studies on pentakis-TTF and trisdeca-TTF derivatives 11 and 3 in dichloromethane solution in the presence of 2,3-dichloronaphthoquinone as an internal reference, show that all the TTF units undergo two single-electron oxidations. The single crystal X-ray structure of compound 7 is reported: the molecules have crystallographic C i symmetry and form chair-like stacks parallel to the crystallographic y axis.

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