Dodecanuclear Hexagonal-Prismatic M12L18 Coordination Cages by Subcomponent Self-assembly

Dodecanuclear hexagonal-prismatic M12L18 cages were prepared by a subcomponent self-assembly process with commercially available pyridinecarboxaldehyde, m-xylenediamine, and cadmium­(II) perchlorate or manganese­(II) perchlorate. The NMR spectrum of the Cd cage shows that there are three independent ligand sets, and the X-ray crystal structure of the Mn cage reveals that the structure has both fac-Δ- and mer-Λ-configured metal centers in a 1:1 ratio. The cage structure also has a large cavity that contains five perchlorate anions.

研究人员通过亚组分自组装工艺，以市售吡啶甲醛、间苯二甲胺以及高氯酸镉(II)或高氯酸锰(II)为起始原料，成功制备得到十二核六方棱柱形M12L18笼状结构。对镉基笼的核磁共振（Nuclear Magnetic Resonance, NMR）谱检测显示，其存在三组独立的配体基团；而锰基笼的X射线晶体结构分析表明，该结构以1:1的比例同时存在面式Δ-和经式Λ-构型的金属中心，且此笼状结构还拥有一个可容纳五个高氯酸根阴离子的大型空腔。