The construction of the head-to-tail tetrameric architecture of TEQs commenced with the synthesis of 16-membered macrocyclic diamide 5 as a key intermediate (Fig. ). Chemoselective lithiation of 2-chloro-8-bromoquinoline and subsequent quenching with gaseous CO2 installed a carboxylic unit at the 8 position, which was capped with a methyl group using trimethylsilyldiazomethane to afford methyl ester 2. A Pd-catalysed Suzuki-Miyaura cross-coupling of 2 with 2-aminophenylboronic acid (3) gave 4, which bears an aniline unit at the 2 position . The judicious choice of using NaHMDS as a base enabled high-yield dimerization via two-fold amidation in THF, furnishing cyclic diamide 5 with the 16 atoms required for the TEQ architecture. The subsequent ring reinforcement reaction en route to TEQ was highly dependent on the pyridine base used for the formation of the iminotriflate. Treatment of 5 with Tf2O, 2-chloropyridine (Py 1 ), and p-anisylacetylene (6) according to Movassaghi's protocol for the formation of pyridine furnished the TEQ architecture , while the yield of 8a was low (5%) and varying amounts of the unexpected dicationic salt 7 were produced via two-fold intramolecular cyclization. The non-planar saddle-shaped 3D structure of 7 was unequivocally determined using single-crystal X-ray diffraction analysis, which revealed a dimeric diazachrysene (ddc) structure with a bent diazacyclooctatetraene core. To prevent the intramolecular nucleophilic cyclization of the quinoline nitrogen atoms, the more electron-rich 2,6-dimethoxypyridine (Py 2 ) was employed instead of Py 1 to increase the fraction of pyridinium intermediate INT-III, improving the yield of TEQ 8a to 25%. The yield of 8a was further increased (44%) when using the even more electron-rich 2,4,6-trimethoxypyridine (Py 3 ).