Cross-catenation between position-isomeric metallacages

Yiliang Wang, Taotao Liu, Yang-Yang Zhang, Bin Li, Liting Tan, Chunju Li (), Xing-Can Shen () and Jun Li
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Yiliang Wang: Guangxi Normal University
Taotao Liu: Guangxi Normal University
Yang-Yang Zhang: Southern University of Science and Technology
Bin Li: Tianjin Normal University
Liting Tan: Guangxi Normal University
Chunju Li: Tianjin Normal University
Xing-Can Shen: Guangxi Normal University
Jun Li: Southern University of Science and Technology

Nature Communications, 2024, vol. 15, issue 1, 1-8

Abstract: 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.

Date: 2024
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DOI: 10.1038/s41467-024-45681-6

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