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.

中文翻译：

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M6L12双链大环化合物的配位性质：高氯酸盐、水和乙腈的共配体竞争取决于金属(II)离子


M(ClO ₄ ) ₂ (M(II) = Mn(II)、Co(II)、Ni(II)、Cu(II) 和 Zn 的自组装(II))与二环戊基二(吡啶-3-基)硅烷(L)作为供体在乙腈和甲苯的混合物中产生由M ₆ L ₁₂ 双链组成的晶体大环化合物。 M(II)阳离子周围的几何形状是典型的八面体排列，但金属大环的外轴配位环境对M(II)阳离子敏感。独特的金属大环的构象在信息上取决于M(II)阳离子周围的配位性质，通过高氯酸根阴离子、水和乙腈之间微妙的共配体竞争。在170°C时，配位乙腈和晶体的溶剂化物分子都被去除，从而将晶体转化为新晶体，并在甲苯和乙腈的混合物中恢复到其原始形式。 [Cu ₆ (ClO ₄ ) ₈ (CH ₃ CN) 催化氧化 3,5-二叔丁基儿茶酚 ₄ L ₁₂ ]4ClO ₄ ·5C ₇ H ₈ 比使用转化产物的速度快得多，[Cu(ClO ₄ ) ₂ L ₂ ]，以及 Cu(ClO ₄ ) ₂