Enantiomerically Pure Trinuclear Helicates via Diastereoselective Self-Assembly and Characterization of Their Redox Chemistry

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• 作者：Christoph G眉tz ; Rainer Hovorka ; Niklas Struch ; Jens Bunzen ; Georg Meyer-Eppler ; Zheng-Wang Qu ; Stefan Grimme ; Filip Topi膰 ; Kari Rissanen ; Mario Cetina ; Marianne Engeser ; Arne L眉tzen
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：August 20, 2014
• 年：2014
• 卷：136
• 期：33
• 页码：11830-11838
• 全文大小：522K
• ISSN：1520-5126

文摘

A tris(bipyridine) ligand 1 with two BINOL (BINOL = 2,2鈥?dihydroxy-1,1鈥?binaphthyl) groups has been prepared in two enantiomerically pure forms. This ligand undergoes completely diastereoselective self-assembly into D₂-symmeteric double-stranded trinuclear helicates upon coordination to copper(I) and silver(I) ions and to D₃-symmetric triple-stranded trinuclear helicates upon coordination to copper(II), zinc(II), and iron(II) ions as demonstrated by mass spectrometry, NMR and CD spectroscopy in combination with quantum chemical calculations and X-ray diffraction analysis. According to the calculations, the single diastereomers that are formed during the self-assembly process are strongly preferred compared to the next stable diastereomers. Due to this strong preference, the self-assembly of the helicates from racemic 1 proceeds in a completely narcissistic self-sorting manner with an extraordinary high degree of self-sorting that proves the power and reliability of this approach to achieve high-fidelity diastereoselective self-assembly via chiral self-sorting to get access to stereochemically well-defined nanoscaled objects. Furthermore, mass spectrometric methods including electron capture dissociation MSⁿ experiments could be used to elucidate the redox behavior of the copper helicates.