Aromatic Pathways of Porphins, Chlorins, and Bacteriochlorins

Abstract

Magnetically induced current densities have been calculated for free-base porphynoids using the gauge including magnetically induce current (GIMIC) method. Numerical integration of the current density passing selected chemical bonds yields current pathways and the degree of aromaticity according to the magnetic criterion. The ring-current strengths of the porphins, chlorins, and bacteriochlorins are 1.5–2.5 times stronger than for benzene. The calculations show that the 18π [16]­annulene inner cross is not the correct picture of the aromatic pathway for porphyrins. All conjugated chemical bonds participate in the current transport independently of the formal number of π electrons. The ring current branches at the pyrrolic rings taking both the outer and the inner route. The NH unit of the pyrrolic rings has a larger resistance and a weaker current strength than the pyrroles without inner hydrogens. The traditional 18π [18]­annulene with inactive NH bridges is not how the ring-current flows around the macroring. The porphins have the strongest ring current of ca. 27 nA/T among the investigated porphynoids. The current strengths of the chlorins and bacteriochlorins are 19–24 nA/T depending on whether the ring current is forced to pass an NH unit or not. The current strengths of the 3-fold and 4-fold β-saturated porphynoids are 13–17 nA/T, showing that the inner-cross 18π [16]­annulene pathway is not a preferred current route