The Power of Packing: Metallization of an Organic Semiconductor

Benzoquino-bis-1,2,3-dithiazole 5 is a closed shell, antiaromatic 16 pi-electron zwitterion with a small HOMO-LUMO gap. Its crystal structure consists of planar ribbon-like molecular arrays packed into offset layers to generate a brick-wall motif with strong 2D interlayer electronic interactions. The spread of the valence and conduction bands, coupled with the narrow HOMO-LUMO gap, affords a small band gap semiconductor with sigma(RT) = 1 X 10(-3) S cm(-1) and E-act = 0.14 eV for transport within the brick-wall arrays. Closure of the band gap to form an all-organic molecular metal with sigma(RT) > 10(1) S cm(-1) can be achieved by the application of pressure to 8 GPa.