Abstract

The important and perspective molecular building blocks composed of hexaphenylbenzenes (HPBs) or their oxidized derivatives, hexa-peri-hexabenzocoronenes (HBCs), and metalloporphyrins have recently received significant attention of the researchers. In this study, motivated by recent findings, we have addressed the modifications of structures and properties of HBC-porphyrin compounds by using instead of aromatic porphyrins antiaromatic 20πisophlorin derivatives of thiophene or selenophene. We have reported the first comparative computational investigation of the following systems: (i) HBC with one non-metallated aromatic porphyrin, P(N4H2), unit, HBC-P(N4H2), (ii) HBC with one S-core-modified antiaromatic porphyrin (S-isophlorin), PS4, unit, HBC-PS4, and (iii) HBC with one Se-core-modified antiaromatic porphyrin (Se-isophlorin), PSe4, unit, HBC-PSe4. The study has been done employing the B3LYP/6-31G∗ approach (in the gas phase and in the implicit solvents, benzene and dichloromethane), and comparison with the B3LYP/6-31G∗∗ and B3LYP/6-311G∗ approaches was performed, where relevant. The effects of the core-modified antiaromatic isophlorins on the structures, electronic, and other properties, potentially including reactivity, of the whole building block HBC-isophlorin have been shown to be quite pronounced and to be noticeably stronger than the effects of the original aromatic non-metallated porphyrin. Thus, we have demonstrated theoretically that the complete porphyrin core-modification with other elements, this time with S and Se leading to the formation of the antiaromatic isophlorins, should be considered as a promising way for modifying and tuning structures, electronic properties and reactivity of the hexabenzocoronene-porphyrin(s) building blocks.