The four-electron diamagnetic ring current of porphycene

Abstract

Porphycene, an isomer that can replace porphin in chemical and biochemical contexts, is predicted by ab initio calculation to exhibit a global diatropic π ring current with bifurcation across the four pyrrole units of the macrocycle. Analysis of the orbital contributions to the current density in porphycene reveals that the global current, with its bifurcation feature, is attributable to the four electrons of the near-degenerate HOMO levels, the same set of active electrons that feature in the well-known four-orbital model of the electronic spectra of porphyrins. Integration of the current density gives ¹H, ¹³C and ¹⁵N NMR shieldings that are compatible with the observed low-field shifts of peripheral and bridge protons and high-field shift of the internal NH protons, assignment of the ¹³C NMR spectrum and the single average ¹⁵N chemical shift resulting from rapid NH tautomerism. Geometries were calculated with the DFT B3LYP functional, the current density maps were calculated with the ipsocentric coupled-Hartree–Fock CTOCD-DZ method, and the shieldings with the CTOCD-PZ2 variant, all in the same 6-31G** basis.