π-Radical Cationic Salts of Tetrathiafulvalene Derivatives with Pyromellitate
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Pyromellitate is known to form hydrogen-bonding anionic networks when the number of deprotonation from pyromellitic acid is one or two. This unique anion has been utilized for the construction of the π-radical cationic salts of the tetrathiafulvalene (TTF) derivatives. In the crystals of three kinds of the TTF salts and the tetramethyltetraselenafulvalene salt, pyromellitate was found to form two-dimensional sheets. The anions in the two TTF salts were connected by rhombic-type inter-anionic connection, which is a typical inter-anionic connection pattern for pyromellitate. The TTF derivatives were all in a π-radical mono-cationic state and dimerized in a space dictated by the anionic networks. The extra space in the crystals was filled with crystal solvents. On the other hand, in the crystals of the ethylenedithia-tetrathiafulvalene salts, pyromellitate formed only intra-molecular hydrogen bonds. The anion was thus isolated in these crystals.
- Bull. Chem. Soc. Jpn.
Bull. Chem. Soc. Jpn. 80(3), 476-483, 2007-03-15
The Chemical Society of Japan