Coordination-Driven Selective Formation of D2 Symmetric Octanuclear Organometallic Cages |
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Authors: | Dr Long Zhang Dr Yue-Jian Lin Prof Zhen-Hua Li Prof J Fraser Stoddart Prof Guo-Xin Jin |
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Institution: | 1. State Key Laboratory of Molecular Engineering of Polymers, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, 2005 Songhu Road, Shanghai, 200433 P.R. China;2. Department of Chemistry, Northwestern University, Evanston, Illinois, 60208 United States |
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Abstract: | The coordination-driven self-assembly of organometallic half-sandwich iridium(III)- and rhodium(III)-based building blocks with asymmetric ambidentate pyridyl-carboxylate ligands is described. Despite the potential for obtaining a statistical mixture of multiple products, D2 symmetric octanuclear cages were formed selectively by taking advantage of the electronic effects emanating from the two types of chelating sites – (O,O’) and (N,N’) – on the tetranuclear building blocks. The metal sources and the lengths of bridging ligands influence the selectivity of the self-assembly. Experimental observations, supported by computational studies, suggest that the D2 symmetric cages are the thermodynamically favored products. Overall, the results underline the importance of electronic effects on the selectivity of coordination-driven self-assembly, and demonstrate that asymmetric ambidentate ligands can be used to control the design of discrete supramolecular coordination complexes. |
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Keywords: | ambidentate ligands cage compounds coordination modes isomers self-assembly |
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