Preparative-scale HPLC resolution of syn and anti topoisomers of subphthalocyanine dimers

Subphthalocyanines (SubPcs) are curved [Formula: see text]-conjugated macrocycles that have emerged as versatile scaffolds for optoelectronic applications. Their fusion into oligomeric architectures offers an attractive route to extend conjugation and modulate topology. Yet, the resulting syn and anti topoisomers are challenging to isolate, hindering systematic studies of their structure–property relationships. Herein, we report a preparative high-performance liquid chromatography (HPLC) methodology that enables the efficient resolution of fused SubPc dimers into their individual topoisomers. Using the archetypal F 12 SubPc–Cl dimer as a model system, we established optimal conditions that allow the isolation of up to 144 mg of each isomer per day with excellent purity, far surpassing conventional silica-based protocols. Notably, the HPLC protocol proved broadly applicable to dimers bearing diverse axial substituents — including terminal alkyne, phenol, and halogen groups — demonstrating the robustness and versatility of the method. This work thus establishes preparative HPLC as a powerful and scalable tool for accessing topologically pure SubPc oligomers.