Resonating Valence Bond and σ-Charge Density Wave Phases in a Benzannulated Phenalenyl Radical
2010-03-03T00:00:00Z (GMT) by
We report the preparation of the first benzannulated phenalenyl neutral radical conductor (18), and we show that the compound displays unprecedented solid state behavior: the structure is dominated by two sets of intermolecular interactions: (1) a π-chain structure with superimposed π-overlap of the benzannulated phenalenyls along [0 0 1], and (2) an interchain overlap involving a pair of carbon atoms (C4) along [0 1 0]. The π-chain-type stacking motif is reminiscent of previously reported phenalenyl radicals and the room temperature structure (space group P2/c) together with the conductivity of σRT = 0.03 S/cm and the Pauli-like magnetic susceptibility are best described by the resonating valence bond (RVB) model. The interchain interaction is unstable with respect to the formation of a σ-charge density wave (σ-CDW) involving pairs of C4 carbon atoms between adjacent radicals and this phase is characterized by the P21/c space group which involves a doubling of the unit cell along the [0 1 0] direction. The RVB and CDW phases compete for structural occupancy throughout the whole temperature range (15−293 K) with the RVB phase predominating at 15 and 293 K and the σ-CDW phase achieving a maximum structural occupancy of about 60% at 150 K where it produces clearly discernible effects on the magnetism and conductivity.