C-I...NC halogen bonding in two polymorphs of the mixed-valence 2:1 charge-transfer salt (EDT-TTF-I2)2(TCNQF4), with segregated versus alternated stacks.
Oxidation of diiodoethylenedithiotetrathiafulvalene (EDT-TTF-I2), C8H4I2S6, with the strong oxidizer tetrafluorotetracyanoquinodimethane (TCNQF4), C12F4N4, affords, depending on the crystallization solvent, two polymorphs of the 2:1 charge-transfer salt (EDT-TTF-I2)2(TCNQF4), represented as D2A. In both salts, the TCNQF4 is reduced to the radical anion state, and is associated through short C-I...NC halogen bonds to two EDT-TTF-I2 molecules. The two polymorphs differ in the solid-state association of these trimeric D-A-D motifs. In polymorph (I) the trimeric motif is located on an inversion centre, and hence both EDT-TTF-I2 molecules have +0.5 charge. Together with segregation of the TTF and TCNQ derivatives into stacks, this leads to a charge-transfer salt with high conductivity. In polymorph (II) two crystallographically independent EDT-TTF-I2 molecules bear different charges, close to 0 and +1, as deduced from an established correlation between intramolecular bond lengths and charge. Overlap interactions between the halogen-bonded D(0)-A-∙D+∙ motifs give rise, in a perpendicular direction, to diamagnetic A2(2-) and D(0)-D2(2+)-D(0) entities, where the radical species are paired into the bonding combination of respectively the acceptor LUMOs and donor HOMOs. The strikingly different solid-state organization of the halogen-bonded D-A-D motifs provides an illustrative example of two modes of face-to-face interaction between π-type radicals, into either delocalized, uniform chains with partial charge transfer and conducting behaviour, or localized association of radicals into face-to-face A2(2-) and D2(2+) dyads.
Institut des Sciences Chimiques de Rennes, Université Rennes 1, UMR CNRS 6226, Campus de Beaulieu, 35042 Rennes, France.
Julien
J
Lieffrig
Institut des Sciences Chimiques de Rennes, Université Rennes 1, UMR CNRS 6226, Campus de Beaulieu, 35042 Rennes, France.
Olivier
O
Jeannin
Institut des Sciences Chimiques de Rennes, Université Rennes 1, UMR CNRS 6226, Campus de Beaulieu, 35042 Rennes, France.
Antoine
A
Vacher
Institut des Sciences Chimiques de Rennes, Université Rennes 1, UMR CNRS 6226, Campus de Beaulieu, 35042 Rennes, France.
Dominique
D
Lorcy
Laboratoire de Physique des Solides, Université Paris-Sud, UMR CNRS 8502, Bât. 510, 91405 Orsay, France.
Pascale
P
Auban-Senzier
Institut des Sciences Chimiques de Rennes, Université Rennes 1, UMR CNRS 6226, Campus de Beaulieu, 35042 Rennes, France.
Marc
M
Fourmigué
charge-transfer salt; radical species; solid state