Effects of fluorination on electronic and excited states of fused zinc oligoporphyrins

Density functional theory (DFT) has been applied to study the effect of fluorination on the electronic and excited states of fused zinc oligoporphyrins in the search for new functionalizing materials, such as n-type organic semiconductors. The excitation spectra of meso-tetrafluoro, beta-octafluoro, and perfluoro zinc porphyrins, and their triply meso-meso-, beta-beta, and beta-beta-linked fluorinated zinc oligoporphyrins were systematically examined using the time-dependent DFT method. The effect of the perfluorination on the zinc porphyrin (ZnP) causes the maximum 1.12 eV and 1.42 eV drops for the highest occupied and lowest unoccupied molecular orbital (HOMO and LUMO, respectively) levels, respectively. The electronic and excitation features of the fluorinated ZnPs are almost similar to the unfluorinated ones. However, the large antibonding contribution of the meso-fluorines disturbs the stabilization of the HOMO, resulting in a more effective reduction of both the HOMO-LUMO gaps and the lowest Q excitation energies with the increasing number of porphyrins compared to the unfluorination and the other types of fluorinations. It is found that the infinite fused fluorinated ZnP tapes with narrow gap (approximately = 0.1 eV-0.2 eV) as predicted by using the periodic-DFT level are slightly inferior to the near-zero gap semimetallic unfluorinated ZnP tape as a conducting molecular wire. The combination of the condensation and the meso- and/or beta-fluorination of ZnP can finely tune the LUMO level to the Fermi level of the electrodes for fabrication of n-type conducting materials. The fused fluoro-oligoporphyrins may then become new n-type organic semiconductors, provided they are well crystallized with a high electron mobility, such as the recently synthesized perfluoropentacene.