Trefoil-shaped metallacycle and metallacage via heteroleptic self-assembly |
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| Institution: | 1. 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;2. 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 410083, China;3. College of Chemistry and Chemical Engineering, Qiannan Normal University for Nationalities, Duyun 558000, China;4. Materials Chemistry & Engineering Laboratory, Department of Polymer Science & Engineering, Dankook University, Yongin, Gyeonggi-do 16890, South Korea;1. College of Chemical Engineering, Sichuan University of Science & Engineering, Zigong, 643000, China;2. College of Chemistry, Sichuan University, Chengdu, 610064, China;3. Zhejiang nhu pharmaceutical co.ltd, Shaoxing, 312000, China;4. Comprehensive Analysis Center, ISIR, Osaka University, Osaka, 567-0047, Japan;1. School of Chemical Engineering and Technology, Department of Chemical Engineering, Shaanxi Key Laboratory of Energy Chemical Process Intensification, Xi''an Jiao Tong University, Xi''an 710049, China;2. School of Stomatology, State Key Laboratory of Military Stomatology & National Clinical Research Center for Oral Diseases & Shaanxi Clinical Research Center for Oral Diseases, Department of Preventive Dentistry, The Fourth Military Medical University, Xi''an 710032, China;3. School of Stomatology, State Key Laboratory of Military Stomatology, Department of Oral and Maxillofacial Surgery, The Fourth Military Medical University, Xi''an 710032, China;4. Department of Prosthodontics, Peking University School and Hospital of Stomatology, National Clinical Research Center for Oral Diseases, National Engineering Laboratory for Digital and Material Technology of Stomatology, Beijing Key Laboratory of Digital Stomatology, Beijing 100081, China;5. School of Stomatology, State Key Laboratory of Military Stomatology, National Clinical Research Center for Oral Diseases, Shaanxi International Joint Research Center for Oral Diseases, Center for Tissue Engineering, The Fourth Military Medical University, Xi''an 710032, China;1. School of Chemical Engineering and Technology, Xi''an Jiaotong University, Xi''an 710049, China;2. State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China;3. School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, Singapore 637371, Singapore;1. MOE Laboratory of Bioinorganic and Synthetic Chemistry, Lehn Institute of Functional Materials, School of Chemistry, Sun Yat-sen University, Guangzhou, 510006, China;2. Institute of Environmental Research at Greater Bay Area, Guangzhou University, Guangzhou, 510006, China;3. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032, China;1. College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Key Laboratory of Organosilicon Material Technology, Hangzhou Normal University, Hangzhou 311121, China;2. Stoddart Institute of Molecular Science, Department of Chemistry, Zhejiang University, Hangzhou 310027, China;3. Green Catalysis Center and College of Chemistry, Zhengzhou University, Zhengzhou 450001, China |
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| Abstract: | Template-oriented multi-component synthesis method has been proven to be an exceedingly reasonable and excellent method for the synthesis of giant two-dimensional (2D) and three-dimensional (3D) supramolecules, but designing and constructing heteroleptic and controllable self-assembly without unexpected by-products remains a challenge. Here we report two discrete trefoil-shaped metallacycle S1 and metallacage S2 by heteroleptic self-assembly using one hexaphenylbenzene core ligand and two capping ligands. The 2D trefoil-shaped metallacycle S1 could resemble the emblem of the classic ‘Mitsubishi’ motif. The use of template-oriented ligand and bent spacer ligand promotes the quantitative formation of the desired 3D trefoil-shaped metallacage S2. The formed metallacage S2 possesses a molecular weight up to 36 kDa, diameter 6.6 nm and height 3.0 nm. All supramolecular coordination complexes were fully characterized by NMR spectroscopy (1H NMR, 2D COSY, 2D NOESY, 2D DOSY), high-resolution electrospray ionization mass spectrometry ESI-MS, ESI-TWIM-MS, TEM and AFM. |
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