Selective Construction and Structural Transformation of Homogeneous Linear Metalla[4]catenane and Metalla[2]catenane Assemblies

• Published in: Angewandte Chemie 2024-04, Vol.136 (18), p.n/a
• Main Authors: Shan, Wei‐Long, Hou, Huan‐Huan, Si, Nian, Wang, Cai‐Xia, Yuan, Guozan, Gao, Xiang, Jin, Guo‐Xin
• Format: Article
• Language: English
• Subjects: Half-Sandwich Complexes; Metallacatenanes; Rhodium; Self-Assembly
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.202402198

Although the synthesis of mechanically interlocked molecules has been extensively researched, selectively constructing homogeneous linear [4]catenanes remains a formidable challenge. Here, we selectively constructed a homogeneous linear metalla[4]catenane in a one‐step process through the coordination‐driven self‐assembly of a bidentate benzothiadiazole derivative ligand and a binuclear half‐sandwich rhodium precursor. The formation of metalla[4]catenanes was facilitated by cooperative interactions between strong sandwich‐type π‐π stacking and non‐classical hydrogen bonds between the components. Moreover, by modulating the aromatic substituents on the binuclear precursor, two homogeneous metalla[2]catenanes were obtained. The molecular structures of these metallacatenanes were unambiguously characterized by single‐crystal X‐ray diffraction analysis. Additionally, reversible structural transformation between metal‐catenanes and the corresponding metallarectangles could be achieved by altering their concentration, as confirmed by mass spectrometry and NMR spectroscopy studies. A homogeneous linear metalla[4]catenane consisting of four linked rings was obtained in a one‐step process through the coordination‐driven self‐assembly of a bidentate benzothiadiazole derivative ligand and a binuclear Cp*Rh‐based precursor.