Description of Aromaticity in Porphyrinoids

Like the larger nonplanar Möbius rings, porphyrinoid aromaticity is not due primarily to the macrocyclic π conjugation of the corresponding annulene perimeters. The block-localized wave function (BLW)-derived aromatic stabilization energies (ASE) of several porphyrinoids reveal that, on a per atom basis, the appended 6π electron heterocycles of porphyrinoids confer aromaticity much more effectively than the macrocyclic 4<i>n</i>+2 π electron conjugations. There is no direct relationship between thermochemical stability of porphyrinoids and their macrocyclic 4<i>n</i> or 4<i>n</i>+2 π electron counts. Porphyrinoids having an “antiaromatic” macrocyclic 4<i>n</i>+2 π electron conjugation pathway (e.g., <b>4</b>) as well as those having no macrocyclic conjugation (e.g., <b>9</b>) can be stabilized by aromaticity. Computed nucleus independent chemical shifts (NICS) and the anisotropy of the induced current density (ACID) disclose the intricate local versus macrocyclic circulation interplay for several porphyrinoids