Fine Tuning the Performance of Multiorbital Radical Conductors by Substituent Effects
journal contributionposted on 24.01.2017, 18:23 by Aaron Mailman, Joanne W. L. Wong, Stephen M. Winter, Robert C. M. Claridge, Craig M. Robertson, Abdeljalil Assoud, Wenjun Yong, Eden Steven, Paul A. Dube, John S. Tse, Serge Desgreniers, Richard A. Secco, Richard T. Oakley
A critical feature of the electronic structure of oxobenzene-bridged bisdithiazolyl radicals 2 is the presence of a low-lying LUMO which, in the solid state, improves charge transport by providing additional degrees of freedom for electron transfer. The magnitude of this multiorbital effect can be fine-tuned by variations in the π-electron releasing/accepting nature of the basal ligand. Here we demonstrate that incorporation of a nitro group significantly stabilizes the LUMO, and hence lowers Ueff, the effective Coulombic barrier to charge transfer. The effect is echoed, at the molecular level, in the observed trend in Ecell, the electrochemical cell potential for 2 with R = F, H and NO2. The crystal structures of the MeCN and EtCN solvates of 2 with R = NO2 have been determined. In the EtCN solvate the radicals are dimerized, but in the MeCN solvate the radicals form superimposed and evenly spaced π-stacked arrays. This highly 1D material displays Pauli-like temperature independent paramagnetic behavior, with χTIP = 6 × 10–4 emu mol–1, but its charge transport behavior, with σRT near 0.04 S cm–1 and Eact = 0.05 eV, is more consistent with a Mott insulating ground state. High pressure crystallographic measurements confirm uniform compression of the π-stacked architecture with no phase change apparent up to 8 GPa. High pressure conductivity measurements indicate that the charge gap between the Mott insulator and metallic states can be closed near 6 GPa. These results are discussed in the light of DFT band structure calculations.
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8 GPanitro groupχ TIPFine Tuningphase changeDFT band structure calculationscharge transferU eff6 GPaSubstituent EffectsE actE cellLUMOelectrochemical cellbasal ligand0.05 eVMeCN solvateelectron transferEtCN solvatesoxobenzene-bridged bisdithiazolyl radicals 2High pressure conductivity measurementsuniform compressionCoulombic barrierσ RTMott insulatormultiorbital effectcharge transportπ- electronground stateHigh pressurecrystal structurescharge transport behavior1 D material displays Pauli-like temperatureEtCN solvateMultiorbital Radical Conductorscharge gapradicals form