Role of the Open-Shell Character on the Pressure-Induced Conductivity of an Organic Donor-Acceptor Radical Dyad

Chemistry : a European Journal
Manuel SoutoJaume Veciana

Abstract

Single-component conductors based on neutral organic radicals have received a lot of attention due to the possibility that the unpaired electron can serve as a charge carrier without the need of a previous doping process. Although most of these systems are based on delocalized planar radicals, we present here a nonplanar and spin localized radical based on a tetrathiafulvalene (TTF) moiety, linked to a perchlorotriphenylmethyl (PTM) radical by a conjugated bridge, which exhibits a semiconducting behavior upon application of high pressure. The synthesis, electronic properties, and crystal structure of this neutral radical TTF-Ph-PTM derivative (1) are reported and implications of its crystalline structure on its electrical properties are discussed. On the other hand, the non-radical derivative (2), which is isostructural with the radical 1, shows an insulating behavior at all measured pressures. The different electronic structures of these two isostructural systems have a direct influence on the conducting properties, as demonstrated by band structure DFT calculations.

References

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Citations

Sep 14, 2018·Chemistry : a European Journal·Feng-Wei GaoZhong-Min Su

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