Three internally 1, 3-arylene-bridged azacalix [6] aromatics 1–3 were synthesized by the Pd- catalyzed macrocyclic fragment coupling reaction between a stellated dibrominated pentamer and N 2, N 6-dimethylpyridine-2, 6-diamine or N 1, N 3-dimethylbenzene-1, 3- diamine. Single-crystal X-ray analysis revealed that these bimacrocyclic compounds all adopt a triply pillared groove-shaped conformation, conceptually being derived from the ...