10.1021/ja908768a.s009
Pradip Bag
Pradip
Bag
Mikhail E. Itkis
Mikhail E.
Itkis
Sushanta K. Pal
Sushanta K.
Pal
Bruno Donnadieu
Bruno
Donnadieu
Fook S. Tham
Fook S.
Tham
Hyunsoo Park
Hyunsoo
Park
John A. Schlueter
John A.
Schlueter
Theo Siegrist
Theo
Siegrist
Robert C. Haddon
Robert C.
Haddon
Resonating Valence Bond and σ-Charge Density Wave Phases in a Benzannulated Phenalenyl Radical
American Chemical Society
2010
RVB phase
carbon atoms
benzannulated phenalenyls
CDW phases
conductivity
interchain overlap
150 K
interchain interaction
benzannulated phenalenyl
room temperature structure
compound displays
resonating valence bond
σ RT
occupancy
state behavior
293 K
phenalenyl radicals
unit cell
Benzannulated Phenalenyl RadicalWe report
Resonating Valence Bond
C 4 carbon atoms
2010-03-03 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/Resonating_Valence_Bond_and_Charge_Density_Wave_Phases_in_a_Benzannulated_Phenalenyl_Radical/2787880
We report the preparation of the first benzannulated phenalenyl neutral radical conductor (<b>18</b>), 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 <i>P</i>2/<i>c</i>) together with the conductivity of σ<sub>RT</sub> = 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 <i>P</i>2<sub>1</sub>/<i>c</i> 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.