A Synthetic Journey Toward Functional N ‐Amidophenyl‐Substituted Hexaaza[1 6 ]paracyclophanes

Conjugated macrocycles hold great promises for applications as photo‐ and electroactive materials. In particular, aza‐[1 n ]paracyclophane was recently described to reach high electrical conductivity in single‐crystal devices due to their tubular assemblies. However, the self‐assembly of these macrocycles in solution and in thin films remains a challenge. Our group reported recently that properly‐designed hexaaza[1 6 ]paracyclophane molecules can self‐assemble in nanotubular structures which can delocalize electrons both through bond within the macrocycle and through space along the supramolecular structure. Nevertheless, accessing these macrocyclic molecules with lateral amide moieties is not straightforward. In this paper, we report the various synthetic strategies we designed to access N ‐amidophenyl‐substituted hexaaza[1 6 ]paracyclophane using Cu‐catalyzed Ullmann coupling and Pd‐catalyzed Buchwald–Hartwig reactions as key steps. The synthetic sequences were designed to reach exclusively 6‐membered macrocycles, to limit purification processes to classical column chromatographies, and to provide ~100 mg scale quantities. The optimized synthetic route allowed to study the light‐responsive properties of a 6‐membered triarylamine‐based macrocycle, following procedures originally developed for simpler triarylamine molecules.