Inherently conductive crystals of cyanocobalt(III)phthalocyanine
1987; Elsevier BV; Volume: 19; Issue: 1-3 Linguagem: Inglês
10.1016/0379-6779(87)90447-4
ISSN1879-3290
AutoresYuji Orihashi, Norihisa Kobayashi, Hiroyuki Ohno, E. Tsuchida, Hiro Matsuda, H. Nakanishi, M. Kato,
Tópico(s)Surface Chemistry and Catalysis
ResumoInherently conductive metallophalocyanine crystals were syntheesized by electrolysis. Potassium dicyanocobalt(III)phthalocyanine was electrolyzed at +1.1 V vs. AgAgCl 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 P1, with a = 7.65(3), b = 9.85(4), c = 9.82(3) Å; α = 90.8(3), β = 107.3(3), γ = 107.2(3)°; Fw = 597.5, V = 670.35 Å3, Z = 1, Dx = 1.46, Dm = 1.46 Mg/m3 (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 × 101 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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