摘要： An insight into the electronic structure of the metal-free, unsubstituted, and nonperipherally substituted with electron-donating groups tetraazaporphyrin (H2TAP), phthalocyanine (H2Pc), naphthalocyanine (H2Nc), anthracocyanine (H2Ac) platforms has been gained and discussed on the basis of experimental UV?vis and MCD spectra as well as density functional theory (DFT), time-dependent DFT (TDDFT), and semiempirical ZINDO/S calculations. Experimental data are suggestive of potential crossover behavior between the 11B2u and 11B3u excited states (in traditional D2h notation) around 800 nm. A large array of exchange-correlation functionals were tested to predict the vertical excitation energies in H2TAPs, H2Pcs, H2Ncs, and H2Acs both in gas phase and solution. In general, TDDFT-predicted energies of the Qx and Qy bands and the splitting between them correlate well with the amount of Hartree?Fock exchange present in a speci?c exchange-correlation functional with the long-range corrected LC-BP86 and LC-wPBE functionals providing the best agreement between theory and experiment. The pure GGA (BP86) exchange-correlation functional signi?cantly underestimated, while long-range corrected LC-BP86 and LC-wPBE exchange-correlation functionals and semiempirical ZINDO/S method strongly overestimated the intramolecular charge-transfer (ICT) transitions experimentally observed for -OR, -SR, and -NR2 substituted at nonperipheral position phthalocyanines and their analogues in the 450?650 nm region. The hybrid CAM-B3LYP, PBE1PBE, and B3LYP exchange-correlation functionals were found to be much better in predicting energies of such ICT transitions. Overall, we did not ?nd a single exchange-correlation functional that can accurately (MAD < 0.05 eV) and simultaneously predict the energies and the splittings of the Qx and Qy bands as well as energies of the ICT transitions in a large array of substituted and unsubstituted metal-free phthalocyanines and their benzoannulated analogues.