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Inherently conductive crystals of cyanocobalt(III)phthalocyanine

Synthetic Metals
Publication Date
DOI: 10.1016/0379-6779(87)90447-4
  • Physics


Abstract Inherently conductive metallophalocyanine crystals were syntheesized by electrolysis. Potassium dicyanocobalt(III)phthalocyanine was electrolyzed at +1.1 V vs. AgAgCl reference electrode in acetonitrile solution without any supporting electrolytes. After several hours, single crystals (> 4mm) were grown on the anode surface. Elementary analysis and infrared measurement revealed that these crystals were composed of only cyanocobalt(III)phthalocyanine. The molecular arrangement was estimated by X-ray diffraction analyses. This compound crystallized in the triclinic space group P 1 , with a = 7.65(3), b = 9.85(4), c = 9.82(3) A ̊ ; α = 90.8(3), β = 107.3(3), γ = 107.2(3)°; Fw = 597.5, V = 670.35 A ̊ 3, Z = 1, Dx = 1.46, Dm = 1.46 Mg/ m 3 (by flotation). It turned out that one phthalocyanine molecule is overlapped with adjacent six phthalocyanines, suggesting the three-dimensional overlapping of π-orbitals. The conductivity of this crystals was 5.7 × 10 1 S/cm at room temperature with the activation energy of 0.04 eV. No decay was found after keeping it under atmosphere for several months. Remarkably high concentration of spin at g = 2.008 was observed without temperature dependence, and thermoelectric power of about +40μV/K indicated holes as carrier. The three-dimensional conductive paths might be the reason of high conductivity.

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