Phthalocyanine resonance spectra

Aurous bromide reacts with 1,3-diiminoisoindoline to form a gold-containing phthalocyanine of uncertain formula, having an electron-spin resonance spectrum characteristic of a gold(II) species (189). If properly substantiated, this will be the first divalent gold derivative to be synthesized. 

The most probable order of d levels in copper phthalocyanine is illustrated in Fig. 19 (131, 145). The calculated energies (131) are appended. The relative order of the ea and b2g orbitals is the inverse of that found for copper acetylacetonate (238). Although the data for cobalt phthalocyanine (139) cannot be assigned unambiguously, the orbital levels are probably in the same relative order. The hole would then be in the d orbital rather than in the dxt-yt (as in copper phthalocyanine) and this is in accord with the observation that the electron-spin resonance spectrum of cobalt phthalocyanine is solvent dependent, while that of copper phthalocyanine is not (131, 139). The alternative assignment of the cobalt data places the hole in the dxy orbital lying some 16,000 cm-1 above the dxz,dyX pair, which seems unlikely. 

The proton magnetic resonance spectrum of dipotassium phthalocyanine dicyanoferrate(II) and of an analogous methyl-substituted derivative has been recorded at 60 mc/sec in methanolic potassium cyanide with tetramethylsilane as an internal calibrant 92). 

Fig. 20. The protons responsible for the nuclear magnetic resonance spectrum of phthalocyanine.

Fla. 6. Electron spin resonance spectrum of o-chloranil doped phthalocyanine. Curve represents the first derivative of absorption. 

The macrocyclic phthalocyanine ligand will form a complex Pt(phthalocyanine).1106 The crystal structure shows two polymorphs present because of molecular packing.1107 The platinum is in a square planar coordination geometry with a mean Pt—N distance of 1.98 A. The complex can be partially oxidized with iodine to give conducting mixed valence solids.1108 Eighteen fundamental and overtone combination bands are observed in the resonance Raman spectrum of platinum phthalocyanine, and from this data the symmetry of the excited singlets are found to be Dy.. Qlv or D2.1109... 

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