Synthesis of biomimetic multimetallic clusters is sought after for applications such as efficient storage of solar energy and utilization of greenhouse gases. However, synthetic efforts are hampered by a dearth of ligands that are developed for multimetallic clusters due to current limitations in rational design and organic synthesis. Peptoids, a synthetic sequence-defined oligomer, enable a biomimetic strategy to rapidly synthesize and optimize large, multifunctional ligands by structural design and combinatorial screening. Here we discover peptoid oligomers (≤7 residues) that fold into a single conformation to provide unprecedented tetra- and hexadentate chelation by carboxylates to a [Co₄O₄] cubane cluster. The structures of peptoid-bound cubanes were determined by 2D NMR spectroscopy, and their structures reveal key steric and side-chain-to-main chain interactions that work in concert to rigidify the peptoid ligand. This efficient ligand design strategy holds promise for creating new scaffolds for the abiotic synthesis and manipulation of multimetallic clusters.

中文翻译：

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生物启发的配体设计方法：折叠单链类肽以螯合多金属簇†

寻求仿生多金属簇的合成以用于诸如有效存储太阳能和利用温室气体的应用。然而，由于目前在合理设计和有机合成方面的局限性，为多金属簇开发的配体的缺乏阻碍了合成的努力。类肽（一种合成的序列定义的寡聚物）使仿生策略能够通过结构设计和组合筛选快速合成和优化大型多功能配体。在这里，我们发现类肽寡聚体（≤7个残基）折叠成一个构象，以提供前所未有的四羧酸和六齿螯合作用，并被羧酸盐生成[Co ₄ O ₄]古巴群集。通过2D NMR光谱确定与类肽结合的古巴的结构，它们的结构揭示了关键的空间相互作用以及侧链与主链之间的相互作用，这些相互作用共同作用以增强类肽配体的刚性。这种有效的配体设计策略有望为非生物合成和操纵多金属簇创造新的支架。