Electronic absorption spectra of substituted phthalocyanines in solution and as films

The electronic absorption spectra of several phthalocyanines substituted at the so-called alpha-, beta- and alpha and beta-positions of the macrocycle have been recorded in solution and as films (alpha = 1,4,8,11,15,18,22, and 25 positions or 1,8 (or 11),15 (or 18), and 22 (or 25) positions, and beta = 2,3,9,10,16,17,23, and 24 positions or 2,9 (or 10),16 (or 17), and 23 (or 24) positions). Phthalocyanines substituted with bulky groups at the alpha-positions prevent cofacial aggregation so that their Q-absorption band remains at a similar wavelength both in solution and films, although the film spectra are generally broader. Phthalocyanines substituted at the beta-positions are apt to aggregate cofacially in polar solvents but in films they may show broad Q-bands which spread out to both shorter and longer wavelengths of the solution Q-band, depending on the bulkiness of the substituents. The film spectra of hexadeca-substituted phthalocyanines exhibit Q-bands at a similar wavelength as in solution, with insignificant broadening of the Q-band on film formation. However, the Soret bands for most of the substituted phthalocyanines are shifted and broadened to longer wavelength in the films. Copyright (C) 2003 Society of Porphyrins & Phthalocyanines.