Magnetically Induced Current Densities in π-Conjugated Porphyrin Nanoballs.

Magnetically induced current densities (MICDs) of Zn-porphyrinoid nanostructures have been studied at the density functional theory level using the B3LYP functional and the def2-SVP basis set. Six of the studied Zn-porphyrinoid nanostructures consist of two crossing porphyrinoid belts, and one is a porphyrinoid nanoball belonging to the octahedral () point group. The Zn-porphyrin units are connected to each other via butadiyne linkers as in a recently synthesized porphyrinoid structure resembling two crossed belts. The MICDs are calculated using the gauge-including magnetically induced current method. Current-density pathways and their strengths were determined by numerically integrating the MICD passing through selected planes that cross chemical bonds or molecular rings. The current-density calculations show that the studied neutral molecules are globally nonaromatic but locally aromatic sustaining ring currents only in the individual porphyrin rings or around two neighboring porphyrins. The ring-current strengths of the individual porphyrin rings are 20% weaker than in Zn-porphyrin, whereas oxidation leads to globally aromatic cations sustaining ring currents that are somewhat stronger than for Zn-porphyrin.