A Modified Pyrrole Biscarbinol Approach to <i>Opp</i> ‐A ₂ B ₂ ‐Symmetric Benzoporphyrins

In the pursuit of advanced functional materials, π‐extended porphyrin derivatives, particularly β , β ‐benzannulated tetrapyrroles, have garnered significant attention due to their unique structural and electronic properties. This study refines existing methodologies for the selective synthesis of opp ‐A 2 B 2 ‐symmetric benzoporphyrins based on 4,7‐dihydro‐4,7‐ethano‐2H‐isoindole or [3,4]epipyrroloanthracene building blocks. By condensation of preformed biscarbinols, this approach overcomes regioselectivity challenges in traditional condensation methods, which typically favor other isomers over the desired opp ‐A 2 B 2 regio derivative. The analysis of the resulting C 2v ‐symmetric tetrapyrroles exhibit distinct optoelectronic, electrochemical, and structural properties compared to their fully symmetrical A 4 counterparts, underscoring their potential in organic optoelectronics applications.