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Single-step synthesis of a heterometallic [Cu2PdL4]2+ hybrid metal-organic coordination cage
ChemRxiv Pub Date : 2025-01-03 , DOI: 10.26434/chemrxiv-2024-lfgkf-v2
David, Turner, Shannon, Thoonen, Samuel, Walker, Samuel, Brandon, Kellie, Tuck, James, Crowley, Martin, Paterson, Alasdair, McKay

Traditional methods of assembling low-symmetry heterometallic cage architectures are limited to stepwise construction and combinations of inert and labile metal ions, affording complex, anisotropic cage structures by sacrificing synthetic ease. Herein, a heterometallic [Cu2PdL4]2+ lantern-type cage has been assembled in a single self-assembly step through the use of a heteroditopic ligand with two different metal-binding groups. The resultant cage complex is a fusion of two common lantern-type cage motifs – carboxylate-based metal–organic Cu4L4 cages and pyridyl-based Pd2L4 coordination cages. Evidence for heterometallic cage formation in solution was provided by 1H and DOSY NMR spectroscopy and electrospray ionisation mass spectrometry (ESI-MS) data, while circular dichroism (CD) spectra confirmed the helical nature of the assembly. It is envisioned that the simple design strategy presented herein will ease the assembly of other structurally complex, low-symmetry cage architectures.

中文翻译:


异金属 [Cu2PdL4]2+ 杂化金属-有机配位笼的一步法合成



组装低对称性异金属笼结构的传统方法仅限于惰性和不稳定金属离子的逐步构建和组合,通过牺牲合成的易用性来提供复杂的、各向异性的笼结构。在此,通过使用具有两个不同金属结合基团的异二位配体,在一个自组装步骤中组装了一个异金属 [Cu2PdL4] 2+ 灯笼。所得的笼复合物是两种常见的灯笼型笼基序的融合——羧酸盐基金属有机 Cu4L4 笼和吡啶基 Pd2L4 配位笼。1H 和 DOSY NMR 波谱和电喷雾电离质谱 (ESI-MS) 数据提供了溶液中异金属笼形成的证据,而圆二色谱 (CD) 波谱证实了组装体的螺旋性质。可以设想,本文提出的简单设计策略将简化其他结构复杂、低对称性笼式架构的组装。
更新日期:2025-01-03
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