Self-assembly of bowl-like trinuclear metallo-macrocycles

By employing different diimine complexes and a naphthanoimidazolate (L(1)) or benzoimidazolate (L(2)) anion ligand as linker, a series of trimetallo-macrocycles have been synthesized through a directed self-assembly approach that involves spontaneous deprotonation of the ligands in aqueous solution. Some compounds, namely, [M(3)L(3)](NO(3))(3) (M = (18-crown-6-phen)Pt, 1 or 7; (15-crown-5-phen)Pt, 2; (benzo-24-crown-8-phen)Pt, 8; (benzo-24-crown-8-phen)Pd, 9; (15-crown-5-phen)Pd, 4 or 11; (18-crown-6-phen)Pd, 3 or 10; (dmbpy)Pd, 6 or 14; (bpy)Pd, 5 or 13; (bpy)Pt, 12; (N4-Phen)Pd, 15) were synthesized. In all of these compounds, the L(1)or L(2) anion ligands are in a syn, syn, syn orientation which result in a bowl-like cavity that can serve as a host to bind the methyl of a solvent CH(3)CN within the naphthanoimidazolate or benzoimidazolate-built cavity through C-H...pi hydrogen bonds in the crystal state. The structures are characterized by elemental analysis, (1)H NMR, ESI-MS, and in the cases of 4a, 11, 13, and 14a by single-crystal X-ray diffraction analysis.