We report the preparation, crystallization, and solid-state characterization of a spiro-biphenalenyl radical. The crystal structure shows that the radical is monomeric in the solid state and without intermolecular contacts that fall within the van der Waals atomic separation. Magnetic susceptibility measurements show Curie behavior (1 spin per molecule) throughout the temperature range 10−400 K, confirming the presence of noninteracting spins in the solid. The compound shows a room-temperature conductivity of σ = 0.05 S/cm, the highest yet for a neutral radical conductor. We suggest that the ground state of the radical corresponds to a degenerate Mott−Hubbard insulator. We postulate the presence of delocalized energy bands that are responsible for the transport properties but that are separated from the insulating ground state by an energy gap corresponding to the on-site Coulombic correlation energy. Given the presence of isolated molecules in the crystal lattice, the magnitude of the conductivity, the finding of band transport, and the width of the conduction band (0.5 eV) are unprecedented.

We report the preparation, crystallization, and solid-state characterization of ethyl (3)- and butyl (4)-substituted spiro-biphenalenyl radicals. Both of these compounds are found to be conducting face-to-face pi-dimers in the solid state but with different room-temperature magnetic ground states. At room temperature, 4 exists as a diamagnetic pi-dimer (interplanar separation of approximately 3.1 A), whereas 3 is a paramagnetic pi-dimer (interplanar separation of approximately 3.3 A), and both compounds show phase transitions between the paramagnetic and diamagnetic forms. Electrical resistivity measurements of single crystals of 3 and 4 show that the transition from the high-temperature paramagnetic pi-dimer form to the low-temperature diamagnetic pi-dimer structure is accompanied by an increase in conductivity by about 2 orders of magnitude. This behavior is unprecedented and is very difficult to reconcile with the usual understanding of a Peierls dimerization, which inevitably leads to an insulating ground state. We tentatively assign the enhancement in the conductivity to a decrease in the on-site Coulombic correlation energy (U), as the dimers form a super-molecule with twice the amount of conjugation.