Coordinating nature of M 6 L 12 double-stranded macrocycles: co-ligand competition of perchlorate, water, and acetonitrile depending on metal(II) ions.

Self-assembly of M(ClO 4 ) 2 (M(II) = Mn(II), Co(II), Ni(II), Cu(II), and Zn(II)) with dicyclopentyldi(pyridine-3-yl)silane (L) as a donor in a mixture of acetonitrile and toluene produces crystals consisting of M 6 L 12 double-stranded macrocycles. The geometry around the M(II) cations is a typical octahedral arrangement, but the metallamacrocycles' outer axial coordination environment is sensitive to the M(II) cations. The conformation of the unique metallamacrocycles is informatively dependent on the nature of the coordination around the M(II) cations via subtle co-ligand competition among perchlorate anions, water, and acetonitrile. Both the coordinated acetonitriles and the solvate molecules of the crystals are removed at 170 °C, thereby transforming the crystals into new crystals that return to their original form in the mixture of toluene and acetonitrile. Catalytic oxidation of 3,5-di- tert -butylcatechol using [Cu 6 (ClO 4 ) 8 (CH 3 CN) 4 L 12 ]4ClO 4 ·5C 7 H 8 is much faster than those using the transformed product, [Cu(ClO 4 ) 2 L 2 ], and a simple mixture of Cu(ClO 4 ) 2 + L.