Magnetically induced current densities and strengths of currents passing through selected bonds have been calculated for monophosphorous hexaphyrin ((PO)hp) and for bisphosphorous hexaphyrin ((PO)2hp) at the density functional theory level using our gauge-including magnetically induced current (GIMIC) approach. The current-density calculations yield quantitative information about electron-delocalization pathways and aromatic properties of singly Möbius twisted hexaphyrins. The calculations confirm that (PO)hp sustains a strong diatropic ring current (susceptibility) of 15 nA T-1 and can be considered aromatic, whereas (PO)2hp is antiaromatic as it sustains a paratropic ring current of -10 nA T -1. Numerical integration of the current density passing through selected bonds shows that the current is generally split at the pyrroles into an outer and an inner pathway. For the pyrrole with the NH moiety pointing outwards, the diatropic ring current of (PO)hp takes the outer route across the NH unit, whereas for (PO)2hp, the paratropic ring current passes through the inner CβCβ double bond. The main diatropic ring current of (PO)hp generally prefers the outer routes at the pyrroles, whereas the paratropic ring current of (PO)2hp prefers the inner ones. In some cases, the ring current is rather equally split along the two pathways at the pyrroles. The calculated ring-current pathways do not agree with those deduced from measured 1H NMR chemical shifts.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry