Hexabenzocoronene functionalized with porphyrin and P-core-modified porphyrin: A comparative computational study

Abstract

We have done the first detailed comparative density functional theory (DFT) study of two novel model building blocks composed of HBC linked with regular porphyrin ZnP and its completely P-core-modified counterpart ZnP(P)4. Our study showed that in these models the ZnP moiety remains essentially unchanged both structurally and electronically, whereas the ZnP(P)4 moiety undergoes significant modifications. In both building blocks significant modifications of the frontier orbital energies and gaps compared to the free HBC and free porphyrins are observed. The effects of the ZnP(P)4 unit on the structure and electronic properties of the whole building block are quite pronounced and seem to be stronger than those of ZnP. Apparently, the electronic communication/interaction within the HBC-ZnP(P)4 species could be stronger due to it structural features. Thus, the porphyrin core-modification with other elements can be considered as a promising way for modifying and tuning versatile properties of the hexabenzocoronene-porphyrins building blocks.