Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
J Am Chem Soc. 2023 May 10;145(18):9965-9969. doi: 10.1021/jacs.3c00661. Epub 2023 Apr 28.
The structural complexity of self-assembled metal-organic capsules can be increased by incorporating two or more different ligands into a single discrete product. Such complexity can be useful, by enabling larger, less-symmetrical, or more guests to be bound. Here we describe a rational design strategy for the use of subcomponent self-assembly to selectively prepare a heteroleptic cage with a large cavity volume (2631 Å) from simple, commercially available starting materials. Our strategy involves the initial isolation of a tris(iminopyridyl) Pd complex , which reacts with tris(pyridyl)triazine ligand to form a heteroleptic sandwich-like architecture . The tris(iminopyridyl) ligand within serves as a "brace" to control the orientations of the labile coordination sites on the Pd centers. Self-assembly of with additional was thus directed to generate a large Pd heteroleptic cuboctahedron host. This new cuboctahedron was observed to bind multiple polycyclic aromatic hydrocarbon guests simultaneously.
自组装的金属有机胶囊的结构复杂性可以通过将两种或更多种不同的配体纳入单个离散产物中来增加。这种复杂性可能很有用，因为它可以允许更大、不对称性更小或更多的客体被结合。在这里，我们描述了一种合理的设计策略，用于使用亚组分自组装来从简单、市售的起始原料中选择性地制备具有大空腔体积（2631 Å）的杂配位笼。我们的策略涉及最初分离出三（亚氨基吡啶基）Pd 配合物，其与三（吡啶基）三嗪配体反应形成杂配位夹心式结构。在 内的三（亚氨基吡啶基）配体充当“支架”以控制 Pd 中心上不稳定配位位点的取向。因此， 与额外的 的自组装被引导生成大的 Pd 杂配位的立方八面体主体。观察到这种新的立方八面体同时结合多个多环芳烃客体。
