The utilization of large ligands in coordination-based self-assembly represents an attractive strategy for the construction of supramolecular assemblies more than two nanometers in size. However, the implementation of this strategy is hampered by the fact that the preparation of such ligands often requires substantial synthetic effort. Herein, we describe a simple one-step protocol, which allows large bipyridyl ligands with a bent shape to be synthesized from easily accessible and/or commercially available starting materials. The ligands were used to construct PdII 2L4-type coordination cages of unprecedented size. Furthermore, we provide evidence that these cages may be stabilized by close intramolecular packing of lipophilic ligand side chains. Packing effects of this kind are frequently encountered in protein assemblies, but they are seldom used as a design element in metallasupramolecular chemistry.
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机译：在基于配位的自组装中利用大配体代表了一种有吸引力的策略，用于构建尺寸超过两纳米的超分子组装。但是，这种策略的实施因以下事实而受到阻碍，即制备此类配体通常需要大量的合成努力。在这里，我们描述了一个简单的一步协议，该协议允许从容易获得和/或可商购的起始原料合成具有弯曲形状的大型联吡啶配体。该配体被用于构建前所未有的Pd II 2L4型配位笼。此外，我们提供的证据表明，这些笼子可以通过亲脂性配体侧链的紧密分子内堆积来稳定。这种堆积效应在蛋白质装配体中经常遇到，但很少用作金属超分子化学中的设计元素。
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