For comparison, two monocyclic octaphyrinoid model compounds, OCT-1 and OCT-2, were also synthesized (Fig. ). Demetalation of compound 5 yielded the free dipyrrin intermediate, which was subsequently complexed with boron trifluoride to form the 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) derivative 9. This "BF₂" coordination was essential for successful intramolecular Yamamoto macrocyclization, as it likely locked the geometry of the dipyrrin subunits, enabling the formation of the targeted macrocycle 10. Oxidative dehydrogenation of 10 using DDQ afforded the fully π-conjugated octaphyrinoid macrocycle OCT-1. The "BF₂" moiety in the BODIPY unit was removed via acid treatment to produce the free octaphyrinoid macrocycle OCT-2. It was found that OCT-2 readily protonated during characterization, and a clean 1 H NMR spectrum could only be obtained in DMSO-d₆. Single-crystal X-ray analysis of it protonated compound [OCT-2+H] + •(SbF6 -) further confirmed its structure (Supplementary Fig. ). In contrast, the [2]catenane 1 exhibited remarkable stability in most common solvents, attributed to strong hydrogen bonding interactions between its interlocked octaphyrinoid macrocycles (vide infra).