Department of Materials Science and Chemical Engineering, Hanyang University, Ansan, Gyeonggi-do 15588, Republic of Korea.
Graduate School of Analytical Science and Technology (GRAST), Chungnam National University, Daejeon 34134, Republic of Korea.
IUCrJ. 2023 May 1;10(Pt 3):321-328. doi: 10.1107/S2052252523002385.
Three novel hierarchical Ni-based metallosupramolecular cages were constructed from nickel ions, pyridine dicarboxylates and isophthalate derivative ligands (the substituents on C5 of isophthalate are methyl, tert-butyl and bromo groups). In every cage, two multinuclear nickel clusters, assembled from four nickel atoms and three pyridine dicarboxylate ligands, are interlinked by three isophthalate-derivative ligands to form a nickel-based triple-stranded helicate (TSH), which then becomes the supramolecular building block for the fabrication of a metallocage. Six homochiral TSH supramolecular building blocks, either left (M)-handed or right (P)-handed, are connected by four linking nickel atoms to generate M and P discrete racemic cage molecules (M - cage with six M-TSHs; P - cage with six P-TSHs). The crystal packing of the racemic cages was characterized by single-crystal X-ray diffraction. An additional cobalt-based molecular cage with 5-methylisophthalate bridging ligands was synthesized for host-guest interaction studies. The methyl groups in Co- and Ni-TSH can act as guest units to be accommodated in the cone-shaped metal clusters (host) of an adjacent cage.
三个新型的镍基超分子笼是由镍离子、吡啶二甲酸酯和间苯二甲酸酯衍生物配体（间苯二甲酸酯的 C5 上的取代基为甲基、叔丁基和溴基）构建而成。在每个笼中，两个由四个镍原子和三个吡啶二甲酸酯配体组装而成的多核镍簇通过三个间苯二甲酸酯衍生物配体相互连接，形成镍基三股螺旋（TSH），然后成为制造金属笼的超分子构建块。六个手性相同的 TSH 超分子构建块，无论是左旋（M）还是右旋（P），通过四个连接镍原子连接，生成 M 和 P 离散外消旋笼分子（M-笼，包含六个 M-TSH；P-笼，包含六个 P-TSH）。外消旋笼的晶体堆积通过单晶 X 射线衍射进行了表征。还合成了一个带有 5-甲基间苯二甲酸酯桥联配体的钴基分子笼，用于主客体相互作用研究。Co-和 Ni-TSH 中的甲基可以作为客体单元，被容纳在相邻笼的锥形金属簇（主体）中。
