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 pi-electron releasing/accepting nature of the basal ligand. Here we demonstrate that incorporation of a nitro group significantly stabilizes the 0 LUMO, and hence lowers U-eff, the effective Coulombic barrier to charge transfer. The effect is echoed, at the molecular level, in the observed trend in E(cel)l, 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 pi-stacked arrays. This highly 1D material displays Pauli-like temperature independent paramagnetic behavior, with chi(TIP) = 6 X 10(-4) emu mol(-1), but its charge transport behavior, with cYRT 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 re-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.