Pressure-Induced Conductivity in a Neutral Nonplanar Spin-Localized Radical.
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.
Institut de Ciència de Materials de Barcelona (ICMAB-CSIC)/CIBER-BBN, Campus Universitari de Bellaterra , 08193 Cerdanyola del Vallès (Barcelona), Spain.
Manuel
M
Souto
Condensed Molecular Materials Laboratory, RIKEN , Wako-shi, Saitama 351-0198, Japan.
HengBo
H
Cui
MALTA CONSOLIDER Team, Departamento de Química Física I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid , 28040 Madrid, Spain.
Miriam
M
Peña-Álvarez
MALTA CONSOLIDER Team, Departamento de Química Física I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid , 28040 Madrid, Spain.
Valentín G
VG
Baonza
Institut für Theoretische Physik, Goethe-Universität Frankfurt , Max-von-Laue-Straße 1, 60438 Frankfurt am Main, Germany.
Harald O
HO
Jeschke
Institut für Theoretische Physik, Goethe-Universität Frankfurt , Max-von-Laue-Straße 1, 60438 Frankfurt am Main, Germany.
Milan
M
Tomic
Institut für Theoretische Physik, Goethe-Universität Frankfurt , Max-von-Laue-Straße 1, 60438 Frankfurt am Main, Germany.
Roser
R
Valentí
Institut de Ciència de Materials de Barcelona (ICMAB-CSIC)/CIBER-BBN, Campus Universitari de Bellaterra , 08193 Cerdanyola del Vallès (Barcelona), Spain.
Davide
D
Blasi
Institut de Ciència de Materials de Barcelona (ICMAB-CSIC)/CIBER-BBN, Campus Universitari de Bellaterra , 08193 Cerdanyola del Vallès (Barcelona), Spain.
Imma
I
Ratera
Institut de Ciència de Materials de Barcelona (ICMAB-CSIC)/CIBER-BBN, Campus Universitari de Bellaterra , 08193 Cerdanyola del Vallès (Barcelona), Spain.
Concepció
C
Rovira
Institut de Ciència de Materials de Barcelona (ICMAB-CSIC)/CIBER-BBN, Campus Universitari de Bellaterra , 08193 Cerdanyola del Vallès (Barcelona), Spain.
Jaume
J
Veciana