The molecular meso-metallaporphyrin has been obtained from the reaction of AlMe3 with the bulky 4,5-(Ph-2(HO)C)(2)-1,2,3-triazole (1). The presence of Al-Me groups coordinated to the triazole rings creates three different stereoisomers that were identified by single-crystal X-ray diffraction. Further studies revealed that, for steric reasons, only one of the two main stereoisomers is active in the polymerization of epsilon-caprolactone. When GaMe3 is used instead of AlMe3, a trimetallic species is formed instead of the meso-metallaporphyrin pointing to a metal-directed self-assembly. On the other hand, the reaction of the monolithium salt [{Li(THF)(2)}{kappa(2)-N,N'-4,5-(Ph-2(HO)C)-1,2,3-triazole}](2) (2; THE = tetrahydrofuran) with MCl3 (M = Al, Ga) yields meso-metallaporphyrin species with a lithium atom in the center of the metallacycle. While the gallium derivative is rather stable in solution, the aluminum analogue decomposes rapidly. In the solid state, continuous cationic columns running throughout the whole crystal are formed from alternating LiC[M](4) (M = Al, Ga) meso-metallaporphyrin and [Li(THF)(4)](+) cations. Density functional theory calculations determined that the weak Cl center dot center dot center dot H, H center dot center dot center dot H, N center dot center dot center dot H, and Cl center dot center dot center dot O interactions with a total interaction energy of -38.6 kcal.mol(-1) are responsible for this unusual packing.