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Selective Synthesis and Structural Transformation of a 4-Ravel Containing Four Crossings and Featuring Cp*Rh/Ir Fragments |
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| Authors: | Li-Long Dang Ting-Ting Zhang Tian Chen Ying Zhao Xiang Gao Francisco Aznarez Prof Lu-Fang Ma Prof Guo-Xin Jin |
| Institution: | 1. College of Chemistry and Chemical Engineering, Luoyang Normal University, Henan Province Function-Oriented Porous Materials Key Laboratory, Luoyang, 471934 P. R. China;2. College of Chemistry and Chemical Engineering, Luoyang Normal University, Henan Province Function-Oriented Porous Materials Key Laboratory, Luoyang, 471934 P. R. China
College of materials and Chemical Engineering, China Three Gorges University, Yichang, 443002 P. R. China These authors contributed equally to this work.;3. State Key Laboratory of Molecular Engineering of Polymers, Department of Chemistry, Fudan University, Shanghai, 200433 P. R. China;4. College of Chemistry and Chemical Engineering, Luoyang Normal University, Henan Province Function-Oriented Porous Materials Key Laboratory, Luoyang, 471934 P. R. China College of materials and Chemical Engineering, China Three Gorges University, Yichang, 443002 P. R. China |
| Abstract: | Intricately interwoven topologies are continually being synthesized and are ultimately equally versatile and significant at the nanoscale level; however, reports concerning ravel structures, which are highly entwined new topological species, are extremely rare and fraught with tremendous synthesis challenges. To solve the synthesis problem, a tetrapodontic pyridine ligand L1 with two types of olefinic bond units and two Cp*M-based building blocks ( E1 , M=Rh; E2 , M=Ir) featuring large conjugated planes was prepared to perform the self-assembly. Two unprecedented 5+10] icosanuclear molecular 4-ravels containing four crossings were obtained by parallel-displaced π⋅⋅⋅π interactions in a single-step strategy. Remarkably, reversible structural transformations between the 4-ravel and the corresponding metallocage could be realized by concentration changes and solvent- and guest-induced effects. X-ray crystallographic data and NMR spectroscopy provide full confirmation of these phenomena. |
| Keywords: | Coordination-Driven Self-Assembly Half-Sandwich Fragment Organometallic Cages π⋅⋅⋅π Interactions 4-Ravel |