P-Type Doping of Stacked Phthalocyanines. Synthesis and Properties of [(MPcF)(z)_y]_x WHERE M=A1 or Ga and Z=BF₄⁻ or PF₆⁻.

Abstract

Nitrosonium salts, NO[Z] where Z = BF₄ ⁻ or PF₆ ⁻, have been used to oxidize the stacked, fluorine bridged metal phthalocyanines (PcMF)_x where M = A1 or Ga. The oxidized products give pressed pellet conductivities as high as 0.3 (ohm-cm)⁻¹. These materials are stable for months in air and only begin to decompose in vacuo at temperatures exceeding 115-125°C. No unpaired spins are observed in the neutral polymers but the oxidized products have highly mobile electrons with spin densities of 0.003 to 0.3 e/anion.

The stacked, fluorine bridged metal phthalocyanine polymers (PcA1F)_x and (pcGaF)_x can be oxidized using nitrosonium salts to give materials with high conductivity. Pure products have excellent air stability and moderately good thermal stability. Incorporation of well characterized stable anions into the materials facilitates reproducibility of experiments and interpretation of physical measurements. ESR measurements demonstrate that the neutral polymers are diamagnetic while the oxidized, conducting products have a moderate number of unpaired spins with high mobilities. All results point toward anti-ferromagnetic interactions among unpaired electrons.