Simultaneous Prediction of the Energies of Q x and Q y Bands and Intramolecular Charge-Transfer Transitions in Benzoannulated and Non-Peripherally Substituted Metal-Free Phthalocyanines and Their Analogues: No Standard TDDFT Silver Bullet Yet.

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 1 1B2u and 1 1B3u 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 Q x and Q y bands and the splitting between them correlate well with the amount of Hartree-Fock exchange present in a specific 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 significantly 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 find a single exchange-correlation functional that can accurately (MAD < 0.05 eV) and simultaneously predict the energies and the splittings of the Q x and Q y bands as well as energies of the ICT transitions in a large array of substituted and unsubstituted metal-free phthalocyanines and their benzoannulated analogues.