Post-functionalization of tritopic subphthalocyanines with C3v symmetry

The successful applications of subphthalocyanines (SubPcs) in the field of molecular materials largely stem from their unique post-functionalization versatility, where regioisomerism and substitution patterns play critical roles. In this context, chiral tritopic [Formula: see text]- or [Formula: see text]-symmetric SubPcs, as well as more symmetric hexatopic C 3v SubPcs, have been extensively explored. However, tritopic derivatives with C 3v symmetry represent an appealing yet underexplored family, combining the lower substitution density of the former with the simplified symmetry of the latter. Herein, we explore the post-functionalization of triimide-SubPcs. Specifically, we synthesize a versatile synthon based on triimide-SubPcs equipped with iodoaryl groups. These SubPcs exhibit high sensitivity under the typical reaction conditions employed for cross-coupling reactions, including Suzuki, Sonogashira, and Buchwald-Hartwig protocols. Nonetheless, we optimize Stille cross-coupling conditions, enabling the selective installation of ethenyl and ethynyl substituents on the aryl groups attached to the imide nitrogen atoms. UV-Vis absorption spectroscopy and theoretical calculations reveal that the ethynyl and ethenyl groups do not significantly alter the electronic structure of the SubPc macrocycle. Collectively, this study establishes a pathway toward the synthesis of the largely unexplored yet highly promising family of C 3v tritopic SubPcs, expanding the toolbox of SubPc derivatives for advanced molecular materials.