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Issue 11, 1999
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Crystal structures and optical properties of cation radical salts of a tetrathiafulvalene trisannulated macrocycle

Abstract

Cation radical salts of the bis(methylthio)tetrathiafulvalene (DMT-TTF) trisannulated macrocycles, [tris(DMT-TTF)]I3 (1) and [tris(DMT-TTF)]IBr2 (2), were prepared and the crystal structures and polarized reflectance spectra of the salts 1 and 2 were investigated. An isostructural character is observed for the two salts. The C3 symmetry of tris(DMT-TTF) bearing three equivalent DMT-TTF units (A, B, and C) within a molecule is broken through the formation of cation radical salts. Two DMT-TTF units (B and C) of three equivalent units form an intramolecular dimer structure through the face-to-face π–π overlap, whereas the plane of the A unit is orthogonal to the dimer plane and isolated from the other units. The intramolecular dimers are further dimerized through the intermolecular B–B′ interaction, resulting in a DMT-TTF tetramer unit (C–B–B′–C′) within the crystal. The intramolecular bond lengths and polarized reflectance spectra indicate the localization of a unit charge on the B unit rather than A or C. The charge separated A0B+C0 electronic structure is confirmed.

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J. Mater. Chem., 1999,9, 2737-2742
Article type
Paper

Crystal structures and optical properties of cation radical salts of a tetrathiafulvalene trisannulated macrocycle

T. Akutagawa, Y. Abe, T. Hasegawa, T. Nakamura, T. Inabe, K. Sugiura, Y. Sakata, C. A. Christensen, J. Lau and J. Becher, J. Mater. Chem., 1999, 9, 2737 DOI: 10.1039/A905362J

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