Issue 23, 2024

Coordinating nature of M6L12 double-stranded macrocycles: co-ligand competition of perchlorate, water, and acetonitrile depending on metal(ii) ions

Abstract

Self-assembly of M(ClO4)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 M6L12 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 [Cu6(ClO4)8(CH3CN)4L12]4ClO4·5C7H8 is much faster than those using the transformed product, [Cu(ClO4)2L2], and a simple mixture of Cu(ClO4)2 + L.

Graphical abstract: Coordinating nature of M6L12 double-stranded macrocycles: co-ligand competition of perchlorate, water, and acetonitrile depending on metal(ii) ions

Supplementary files

Article information

Article type
Paper
Submitted
27 Mar 2024
Accepted
13 May 2024
First published
14 May 2024

Dalton Trans., 2024,53, 9692-9699

Coordinating nature of M6L12 double-stranded macrocycles: co-ligand competition of perchlorate, water, and acetonitrile depending on metal(II) ions

S. An, J. Han, D. Kim, H. Lee and O. Jung, Dalton Trans., 2024, 53, 9692 DOI: 10.1039/D4DT00902A

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