Assignment of the charge-transfer bands in some metal phthalocyanines. Evidence for the S= 1 state of iron (II) phthalocyanine in solution

Abstract
Magnetic circular dichroism spectroscopy has been used to investigate the assignment of the charge transfer bands in a number of metal phthalocyanines containing first row transition metals. It has been shown that the band in cobalt(III) phthalocyanine dicyanide at 22.5 kK is not a charge transfer band but must be a transition of the phthalocyanine ring. Similarly doubt is shed upon the charge-transfer assignment of the band in iron(II) phthalocyanine dicyanide at 22.5 kK. However, it has been confirmed that the band system in cobalt(I) phthalocyanine at ∼22 kK is a metal-ligand charge-transfer transition which may be assigned as egb1u, b2u. Finally, the low energy band of iron(II) phthalocyanine which appears in solvents of low co-ordinating ability, such as dichlorobenzene, has been studied. The m.c.d. spectrum enables a choice to be made for the ground state of the compound. It is shown to be 3A2g, a result which is the first demonstration of an intermediate spinstate of iron(II) in solution. The low energy band in the spectrum has been assigned as a metal to ligand charge transfer band, 3A2g3Eu. This evidence throws considerable doubt upon the recent assignment of the ground state of crystalline iron(II) phthalocyanine to 3B2g based upon single crystal anisotropy measurements.

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