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Electrocrystallization of Metallophthalocyanines: Effects of Substituents on the Oxidation Potential and Crystallization

1988; Taylor & Francis; Volume: 160; Issue: 1 Linguagem: Inglês

10.1080/15421408808083009

1044-1859

Yuji Orihashi, Hiroyuki Ohno, Eishun Tsuchida, Hiro Matsuda, Hachiro Nakanishi, Masao Kato,

Electrocatalysts for Energy Conversion

Abstract A series of oxidation potentials of substituted metallophthalocyanines are examined with cyclic voltammetry. Relation between oxidation potential and the Hammett's constant of substituents is found to be linear for both octa- and tetrasubstituted derivatives. The oxidation potential shift is found to be calculated by electron-withdrawing or donating ability of substituents. Electrocrystallization of these compounds gives crystals which are composed of only cyanometallophthalocyanine. Crystals of substituted derivatives are analyzed to have different molecular arrangements from unsubstituted one because of steric effect of the substituents. Crystals of unsubstituted derivatives show highly inherent conductivity, but substituted ones show less conductivity due to the different molecular arrangements.