The effect of substituents on the position and intensity of the electronic absorption and fluorescence spectra of phthalocyanines (Pcs) was examined for 35 Pc compounds. When electron-releasing groups are bound to four β-benzo positions of the Pc skeleton, the B and Q bands shift to longer wavelength. Relative to this shift, the effect of introducing the same electron-releasing groups at the other four α positions amounts to about 1.6-2.0. Although the effect is not always clearly seen, introduction of electron-releasing groups in the β-benzo positions of the Pc skeleton generally shifts the Q band to shorter wavelength. The effect of electron-with-drawing groups is exactly the opposite with respect to the α and β positions. These effects can be reasonably explained by considering the magnitude of the atomic orbital coefficients of the carbon atoms derived from molecular orbital (MO) calculations. In addition, the following intriguing phenomena were observed in the experiments, although not all were explained theoretically: 1) the splitting of the Q band of metal-free Pcs decreases with increasing wavelength of the Q band, 2) the ring currents of Pcs with Q bands at longer wavelength are generally smaller, and 3) the absorption coefficients of the Q band of Pc compounds with 16-electron-releasing substituents are larger than those of the corresponding tetra- and octasubstituted Pcs by several tens of percent. 4) Our PPP calculations suggested that the absorption coefficient of the Q band of Pcs with more strongly electron releasing substituents is larger. 5) The second HOMO of the Pcs with the Q band at longer wavelength has b1u symmetry, as opposed to the a2u symmetry of normal Pcs. 6) Pcs showing S1 emission maxima at wavelengths longer than about 740 nm generally have quantum yields of less than 0.1.
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