Synthesis of Directly‐Linked Porphyrin−Pyricorrole Hybrid via Rearrangement of Internally‐bridged Octaphyrin(1.1.1.1.1.1.1.1) Upon Ni(II) Metalation

Abstract

A directly-linked Ni II porphyrinÀ Ni II pyricorrole hybrid was obtained upon Ni II complexation of internallybridged octaphyrin(1.1.1.1.1.1.1.1). The structure has been unambiguously revealed by X-ray diffraction analysis. The pyricorrole skeleton is different from that reported earlier with regard to the position of the pyridine moiety. The new pyricorrole macrocycle was characterized as an aromatic molecule sustaining a complex current density. The thermodynamic stability of the Ni II pyricorrole skeleton indicated by DFT calculation may drive this rearrangement.

Tetraquinolines; four linked quinoline units or porphyrinoids

“…Magnetically induced ring current, MICD, has been one of the most used tools for the evaluation of the aromaticity among porphyrinoids. 35–56 Apart from the relevance of the magnetic response properties to the phenomenon of aromaticity, i.e. , stability, 57 some patterns are universal among porphyrinoids.…”

“…, stability, 57 some patterns are universal among porphyrinoids. Even sterically distorted porphyrinoids, 38,45,48–50,52,53,55 or systems in which conjugation is interrupted by an sp 3 carbon, 35 sustain strong diatropic or paratropic global ring currents. In other words, porphyrinoids show a global response to an external magnetic field.…”