Affiliation:
1. Department of Organic and Polymer Chemistry Hunan Key Laboratory of Micro & Nano Materials Interface Science College of Chemistry and Chemical Engineering Central South University Changsha, Hunan 410083 China
2. Department of Physics Old Dominion University Norfolk VA 23529 USA
3. Institute of Environmental Research at Greater Bay Area Key Laboratory for Water Quality and Conservation of the Pearl River Delta Ministry of Education Guangzhou Key Laboratory for Clean Energy and Materials Guangzhou University Guangzhou 510006 China
4. School of Chemistry and Chemical Engineering Henan Normal University Xinxiang Henan 453007 China
Abstract
AbstractCoordination‐driven self‐assembly has been extensively employed for the bottom‐up construction of discrete metallo‐macrocycles. However, the prevalent use of benzene rings as the backbone limits the formation of large metallo‐macrocycles with more than six edges. Herein, by embedding metal nodes into the ligand backbone, we successfully regulated the ligand arm angle and assembled two giant heptagonal metallo‐macrocycles with precise control. The angle between two arms at position 4 of the central terpyridine (tpy) extended after complexation with metal ions, leading to ring expansion of the metallo‐macrocycle. The assembled structures were straightforwardly identified through multi‐dimensional NMR spectroscopy (1H, COSY, NOESY), multidimensional mass spectrometry analysis (ESI‐MS and TWIM‐MS), transmission electron microscopy (TEM), as well as scanning tunneling microscopy (STM). In addition, the catalytic performances of metallo‐macrocycles in the oxidation of thioanisole were studied, with both supramolecules exhibiting good conversion rates. Furthermore, fiber‐like nanostructures were observed from single‐molecule heptagons by hierarchical self‐assembly.
Funder
National Natural Science Foundation of China
Natural Science Foundation of Hunan Province
Fundamental Research Funds for Central Universities of the Central South University
China Postdoctoral Science Foundation