Resonating Valence Bond and σ-Charge Density Wave Phases in a Benzannulated Phenalenyl Radical

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• 作者：Pradip Bag ; Mikhail E. Itkis ; Sushanta K. Pal ; Bruno Donnadieu ; Fook S. Tham ; Hyunsoo Park ; John A. Schlueter ; Theo Siegrist ; Robert C. Haddon
• 刊名：Journal of the American Chemical Society
• 出版年：2010
• 出版时间：March 3, 2010
• 年：2010
• 卷：132
• 期：8
• 页码：2684-2694
• 全文大小：537K
• 年卷期：v.132,no.8(March 3, 2010)
• ISSN：1520-5126

文摘

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 σ_RT = 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.