A 12‐Crossing Vertex‐Fused Double‐Triangle [5]Catenane with Programmed Topological Handedness

Z Zheng Cui L Li‐Yan Hao (Key Laboratory of Green Chemical Media and Reactions (Ministry of Education) Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals School of Chemistry and Chemical Engineering Henan Normal University Xinxiang P. R. China) J Jin‐Ping Chang (Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education College of Chemistry and Materials Science Northwest University Xi'an P. R. China) H Huan‐Huan Li (Key Laboratory of Green Chemical Media and Reactions (Ministry of Education) Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals School of Chemistry and Chemical Engineering Henan Normal University Xinxiang P. R. China) X Xiao‐Peng Xuan (Key Laboratory of Green Chemical Media and Reactions (Ministry of Education) Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals School of Chemistry and Chemical Engineering Henan Normal University Xinxiang P. R. China) G Guang‐Yue Bai (Key Laboratory of Green Chemical Media and Reactions (Ministry of Education) Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals School of Chemistry and Chemical Engineering Henan Normal University Xinxiang P. R. China) Y Ying‐Feng Han (Key State Laboratory of Natural Functional Molecule Chemistry of the Ministry of Education College of Chemistry and Materials Science Northwest University Xi'an People's Republic of China)

Abstract

ABSTRACT High‐crossing mechanically interlocked molecules are attractive because their dense entanglement can encode unusual stereochemistry, but predictable handedness remains difficult to achieve. Here we show that multiple interlocking in coordination‐driven self‐assembly gives access to a 12‐crossing vertex‐fused double‐triangle [5]catenane ( Rh‐2 R ). X‐ray crystallography reveals a composite T(3,3)#T(3,3) topology that can be viewed as two Hopf‐link‐derived T(3,3) units sharing a central tetranuclear ring. The topological handedness of Rh‐2 R tracks the coconformational mechanical helicity of the Hopf‐link motifs, and the opposite ligand enantiomer gives the mirror‐image product both in solution and in the solid state. The solvent composition or concentration shifts the balance between Rh‐2 R and a less entangled Hopf‐linked state ( Rh‑2′ R ), whereas increased ligand steric demand suppresses multiple interlocking. These results reveal that Hopf links can serve as modular stereochemical directors for building and modulating complex topologically chiral links.

Article Details

Volume / Issue Vol. 65, Issue 20
Published May 11, 2026
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (7)

Z

Zheng Cui

L

Li‐Yan Hao

Key Laboratory of Green Chemical Media and Reactions (Ministry of Education) Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals School of Chemistry and Chemical Engineering Henan Normal University Xinxiang P. R. China

J

Jin‐Ping Chang

Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education College of Chemistry and Materials Science Northwest University Xi'an P. R. China

H

Huan‐Huan Li

Key Laboratory of Green Chemical Media and Reactions (Ministry of Education) Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals School of Chemistry and Chemical Engineering Henan Normal University Xinxiang P. R. China

X

Xiao‐Peng Xuan

Key Laboratory of Green Chemical Media and Reactions (Ministry of Education) Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals School of Chemistry and Chemical Engineering Henan Normal University Xinxiang P. R. China

G

Guang‐Yue Bai

Key Laboratory of Green Chemical Media and Reactions (Ministry of Education) Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals School of Chemistry and Chemical Engineering Henan Normal University Xinxiang P. R. China

Y

Ying‐Feng Han

Key State Laboratory of Natural Functional Molecule Chemistry of the Ministry of Education College of Chemistry and Materials Science Northwest University Xi'an People's Republic of China