The α-bromo-thiophene-substituted dipyrrin compound 2 (see Supplementary Information) served as the starting material. Coordination with Zn(II) yielded complex 3 in near-quantitative yield. X-ray crystallography revealed a dihedral angle of about 70° between the dipyrrin units, with terminal α-bromothiophenes oriented in opposite directions (Fig. inset)-a preorganized conformation favorable for interlocked [2]catenane formation. Suzuki-Miyaura coupling of 3 with excess dithiophene-methane-derived boronic ester 4 (see Supplementary Information) produced intermediate 5 in 84% yield. Intramolecular Yamamoto coupling of 5 yielded Zn(II)-complexed interlocked molecule 6 in 24% yield. A doubly twisted figure-eight isomer 7 was also isolated in equal yield due to the flexibility of 5.