Marriage of an N‑Fused and a Regular Porphyrin in a Cofacial Ligand System

We present a straightforward synthetic route which allows cofacial stacking of N-fused porphyrins and regular porphyrins via an o-substituted phenylene linker. The protocol comprises a crucial Suzuki–Miyaura cross-coupling reaction to introduce the phenyl moiety at the tri-pentacyclic ring of the N-fused porphyrin, paving the way to the first arrangement that is capable of holding an N-fused porphyrin and a regular porphyrin in spatial proximity. The ligand system was obtained with a 0.77% yield in five steps, starting from pyrrole and benzaldehyde. The dimeric ligand was investigated for further insights into sterical properties, employing inter alia ion-mobility spectrometry, DFT calculations, and metal coordination reactions. The molecular species were characterized by 1H NMR, UV–vis, IR, high-resolution mass spectrometry, and trapped ion-mobility measurements. The latter suggests that the ligand system can stabilize two atoms of the same metal in different oxidation states, such as in an Mn­(I)­Mn­(III) complex.