X-ray crystallographic analysis of 1-Zn (Fig. ) confirmed its interlocked π-conjugated structure comprising two core-modified octaphyrinoid rings, which are nearly perpendicular to each other, with a dihedral angle of 85.7° (Supplementary Fig. ). All bithiophene subunits adopt a cis configuration, with sulfur atoms oriented inward, significantly expanding the macrocycle size to minimize steric congestion. At the same time, both macrocycles exhibit a slightly curved geometry. The harmonic oscillator model of aromaticity (HOMA) value was calculated to be 0.81 along the 34π-conjugation pathway for both macrocycles (Table ), indicative of global aromaticity following Hückel's rule (aromatic benzene has a HOMA value of 1.0). However, since HOMA values may not reliably characterize large π-conjugated systems, bond-length equalization was further examined. The C-C bonds linking the bridged methine carbons (1-6 and 1′-6′ in Fig. ) range from 1.370 to 1.432 Å with small standard deviations (s.d. = 0.0252 and 0.0272 Å for the two macrocycles, respectively, Table ), supporting aromaticity. The anisotropy of the induced current density (ACID) plots (Fig. ) showed a clockwise diatropic ring current along the periphery of each macrocycle, indicating global aromaticity. The 3D iso-chemical shielding surface (ICSS) 50 map (Fig. ) revealed a strongly shielded chemical environment within the interlocked macrocycles and a deshielded environment outside, further corroborating the global aromatic character of the core-modified octaphyrinoid rings in 1-Zn. The ¹H NMR spectrum of 1-Zn in THF-d₈/CS₂ (1:2, v/v) at 298 K was well-resolved (Fig. ) and fully assigned using 2D NMR techniques. Protons (4-9) on the thiophene units exhibited significant downfield shifts (chemical shift  : 7.96-9.49 ppm) due to the external deshielding effect of the aromatic macrocycle.