Department of Chemistry, The University of Tokyo, Hongo 7-3-1, Bunkyo-ku, Tokyo 113-0033, Japan.
JEOL Resonance Inc., Musashino 3-1-2, Akishima-shi, Tokyo 196-8558, Japan.
J Am Chem Soc. 2021 Sep 22;143(37):15017-15021. doi: 10.1021/jacs.1c08712. Epub 2021 Sep 7.
A method for the synthesis of metal-doped aromatic macrocycles has been developed. The method, i.e., metal-templated oligomeric macrocyclization via coupling, adopts Ni as the template and assembles five pyridine units via a Ni-mediated coupling reaction to form aryl-aryl linkages. A pentameric oligopyridyl macrocycle was selectively obtained in good yield, and the reaction was also applicable to a gram-scale synthesis. The pentameric oligopyridyl macrocycle captured d-Ni(II) at the center to form a paramagnetic pentagonal-bipyramidal complex. The method was applied to the synthesis of a large π-molecule to afford a nanometer-sized, bowl-shaped molecule having a unique combination of 120π and 8d electrons.
一种金属掺杂芳香大环的合成方法已经开发出来。该方法，即通过偶联进行金属模板寡聚大环化，采用 Ni 作为模板，通过 Ni 介导的偶联反应将五个吡啶单元组装在一起，形成芳基-芳基键。五聚吡啶寡环在高收率下选择性得到，反应也适用于克级规模的合成。五聚吡啶寡环在中心捕获 d-Ni(II)，形成顺磁性五边形双锥配合物。该方法还应用于大π分子的合成，得到了一种具有独特的 120π 和 8d 电子组合的纳米级、碗状分子。
