Pressure-Induced Conductivity in a Neutral Nonplanar Spin-Localized Radical
- Scientific Highlights 06 October 2016 4202 hits
Manuel Souto, HengBo Cui, Miriam Peña-Álvarez, Valentín G. Baonza, Harald O. Jeschke, Milan Tomic, Roser Valentí, Davide Blasi, Imma Ratera, Concepció Rovira, and Jaume Veciana*; J. Am. Chem. Soc., 2016, 138 (36), pp 11517–11525
There is a growing interest in the development of single-component molecular conductors based on neutral organic radicals that are mainly formed by delocalized planar radicals, such as phenalenyl or thiazolyl radicals. However, there are no examples of systems based on nonplanar and spin-localized C-centered radicals exhibiting electrical conductivity due to their large Coulomb energy (U) repulsion and narrow electronic bandwidth (W) that give rise to a Mott insulator behavior. Here we present a new type of nonplanar neutral radical conductor attained by linking a tetrathiafulvalene (TTF) donor unit to a neutral polychlorotriphenylmethyl radical (PTM) with the important feature that the TTF unit enhances the overlap between the radical molecules as a consequence of short intermolecular S···S interactions. This system becomes semiconducting upon the application of high pressure thanks to increased electronic bandwidth and charge reorganization opening the way to develop a new family of neutral radical conductors.