Synthesis and self-assembly of triphenylene-containing conjugated macrocycles

Two imine-based shape-persistent macrocycles containing triphenylene building blocks, along with their noncyclic model compounds, have been synthesized. Their stable conformations are predicted by quantum mechanical calculations and confirmed by 2D NOESY NMR measurements. Compared to the noncyclic model compounds, the macrocycles (3 and 6) show a higher propensity for solution self-assembly due to their stronger π-π stacking interactions, and form micro-objects which exhibit an enhanced conductivity after doping. While both macrocycles have identical molecular geometries and very similar structures, their solution self-assembly leads to micro-objects with very different shapes. The two macrocycles also show different pH-dependent optical properties.