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The preparation of anionic phthalocyaninato-cobaltates(III) [CoX 2 Pc(2-)] -  (X = OH . F, CI, Br) is described. The UV -VIS. IR and Resonance-R am an (RR ) spectra are measured and com pared with those of the complexes [CoX 2 Pc(1 -)] (X = Cl, Br) containing the phthalocyanine-π-cation- radical.The characteristic spectroscopical differences for the Pc(1-)- and Pc(2-)-Ligands are discussed. Besides the typical B-, Q- and N-transitions of the Pc(1 -)- and Pc(2 -)-ligand additional weak bands are observed in the UV -VIS spectra for both dichloro- and dibromocomplexes. These bands are assigned to X (π , σ) → Co electron transfer a 2u (π x ), a 2u (σ x ) → a 1g (d); for the Pc(1 - )-complexes Cl(π) is at 22.9, Cl(σ) at 38.9. Br(π-) at 19.6 and Br(σ) at 36.4 kK. For the Pc(2-)-complexes these bands are slightly red-shifted by about 0.5 kK. The assignment is confirm ed by the RR-spectra. For both dichloro- and dibromo-complexes the sym. (Co-X)- stretching vibration (a 1g , ν 1 ) is strongly RR-enhanced and up to four overtones of ν 1  are observed (for Pc(2-): ν ( Co - X ) for X = Cl: 270. Br: 165 cm -1 ; for Pc ( 1 - ) : X = Cl: 280. Br: 168 cm -1 ). The antisym. (Co -X)-stretching vibration (a 2u ) is observed in the FIR spectra (for Pc(2 -): ν(Co-X) for X = F: 546. Cl: 333. Br: 243 cm -1 ; for Pc ( 1 - ) : X = Cl: 326. Br: 250 cm -1 ).

zeitschrift für naturforschung b

Phthalocyanine von Cobalt(III): Darstellung, Resonanz-Raman-, Infrarot- und elektronische Absorptionsspektren von [CoX 2 Pc(1—)] (X = Cl, Br) and [CoX 2 Pc(2-)] -  (X = OH, F, CI, Br)