An ab initio, systematic study on the aromaticity involving the group of metalated extended porphyrins, termed meso-hexakis(pentafluorophenyl)-substitutedhexaphyrin(184.108.40.206.1.1) (HP), was performed for the first time. The aromatic behavior of the system shifted to antiaromatic in the HP analogue, due to the presence of hydrogen atoms that break the orbital symmetry. The absorption bands observed in the experiment were assigned to an intraligand charge transfer, where the intrametallic character is also important. The excited states reveal the absorption of visible light and the possibility of electronic transfer to different systems. We propose a system such as single-walled carbon nanohorns (SWCNHs), due to their special electronic properties, and predict a novel nanohybrid material. The evidence of electronic communication between both species is presented in this work. The HP aromaticity and the spatial configuration of the interaction with SWCNHs are also related to the strength of electronic transfer among the systems, making the HP metalated antiaromatic species and their corresponding nanohybrids potential candidates to be used as building blocks in photovoltaic cell materials. © 2012 Wiley Periodicals, Inc.