Complementary Syntheses Giving Access to a Full Suite of Differentially Substituted Phthalocyanine‐Porphyrin Hybrids

Phthalocyanines and porphyrins are often the scaffolds of choice for use in widespread applications. Synthetic advances allow bespoke derivatives to be made, tailoring their properties. The selective synthesis of unsymmetrical systems, particularly phthalocyanines, has remained a significant unmet challenge. Porphyrin‐phthalocyanine hybrids offer the potential to combine the favorable features of both parent structures, but again synthetic strategies are poorly developed. Here we demonstrate strategies that give straightforward, controlled access to differentially substituted meso‐aryl‐tetrabenzotriazaporphyrins by reaction between an aryl‐aminoisoindolene (A) initiator and a complementary phthalonitrile (B). The choice of precursors and reaction conditions allows selective preparation of 1:3 Ar‐ABBB and, uniquely, 2:2 Ar‐ABBA functionalized hybrids. Two pathways are proposed for the synthesis of an important class of functionalized phthalocyanine‐porphyrin hybrids (TBTAPs). The materials are novel in their own right, but more importantly, the syntheses offer control and variation over structural and substituent modifications, a goal not yet achieved even within the extensively investigated chemistry of the parent phthalocyanines.