Nature Communications (Feb 2024)

Cross-catenation between position-isomeric metallacages

  • Yiliang Wang,
  • Taotao Liu,
  • Yang-Yang Zhang,
  • Bin Li,
  • Liting Tan,
  • Chunju Li,
  • Xing-Can Shen,
  • Jun Li

DOI
https://doi.org/10.1038/s41467-024-45681-6
Journal volume & issue
Vol. 15, no. 1
pp. 1 – 8

Abstract

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Abstract The study of cross-catenated metallacages, which are complex self-assembly systems arising from multiple supramolecular interactions and hierarchical assembly processes, is currently lacking but could provide facile insights into achieving more precise control over low-symmetry/high-complexity hierarchical assembly systems. Here, we report a cross-catenane formed between two position-isomeric Pt(II) metallacages in the solid state. These two metallacages formed [2]catenanes in solution, whereas a 1:1 mixture selectively formed a cross-catenane in crystals. Varied temperature nuclear magnetic resonance experiments and time-of-flight mass spectra are employed to characterize the cross-catenation in solutions, and the dynamic library of [2]catenanes are shown. Additionally, we searched for the global-minimum structures of three [2]catenanes and re-optimized the low-lying structures using density functional theory calculations. Our results suggest that the binding energy of cross-catenanes is significantly larger than that of self-catenanes within the dynamic library, and the selectivity in crystallization of cross-catenanes is thermodynamic. This study presents a cross-catenated assembly from different metallacages, which may provide a facile insight for the development of low-symmetry/high-complexity self-assemble systems.