Evaluation of planarity and aromaticity in sapphyrin and inverted sapphyrin using a bidirectional NICS (Nucleus-Independent Chemical Shift) scan method

Using the bidirectional NICS scan method in conjunction with two-photon absorption (TPA) measurements, it has proved possible to determine the relationship between pi-conjugation and aromaticity in two structurally related expanded porphyrin systems, sapphyrin and inverted sapphyrin, and establish that differences in these defining factors depend on the presence or absence of a key sp(3) hybrid molecular orbital within the macrocyclic periphery.