Thoonen Shannon, Walker Samuel E, Marshall David L, Fulloon Therese M, Brandon Samuel, McKay Alasdair I, Paterson Martin J, Mullen Kathleen M, Crowley James D, Tuck Kellie L, Turner David R
School of Chemistry, Monash University, Clayton, VIC 3800, Australia.
Centre for Materials Science (CFMS), Queensland University of Technology (QUT), 2 George Street, Brisbane, QLD 4000, Australia.
Angew Chem Int Ed Engl. 2025 Jun 2;64(23):e202506064. doi: 10.1002/anie.202506064. Epub 2025 Apr 17.
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 [CuPdL] 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 CuL cages and pyridyl-based PdL coordination cages. Evidence for heterometallic cage formation in solution was provided by H and diffusion-ordered NMR spectroscopy and electrospray ionization mass spectrometry (ESIMS) data, whereas circular dichroism (CD) spectra confirmed the helical nature of the assembly. The heterometallic cage was then exploited in binding heterotopic guests. It is envisioned that the simple design strategy presented herein will ease the assembly of other structurally complex, low-symmetry cage architectures.
组装低对称性异金属笼状结构的传统方法仅限于逐步构建以及惰性和活性金属离子的组合，通过牺牲合成简便性来提供复杂的各向异性笼状结构。在此，通过使用具有两个不同金属结合基团的异二齿配体，在单个自组装步骤中组装了一种异金属[CuPdL]灯笼型笼。所得的笼状配合物是两种常见灯笼型笼基序的融合——基于羧酸盐的金属有机CuL笼和基于吡啶基的PdL配位笼。H和扩散有序核磁共振光谱以及电喷雾电离质谱（ESIMS）数据提供了溶液中异金属笼形成的证据，而圆二色性（CD）光谱证实了组装体的螺旋性质。然后将该异金属笼用于结合异位客体。可以设想，本文提出的简单设计策略将简化其他结构复杂的低对称性笼状结构的组装。
