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

2014; American Chemical Society; Volume: 136; Issue: 33 Linguagem: Inglês

10.1021/ja506327c

1943-2984

Christoph Gütz, Rainer Hovorka, Niklas Struch, Jens Bunzen, Georg Meyer‐Eppler, Zheng‐Wang Qu, Stefan Grimme, Filip Topić, Kari Rissanen, Mario Cetina, Marianne Engeser, Arne Lützen,

DNA and Nucleic Acid Chemistry

A tris(bipyridine) ligand 1 with two BINOL (BINOL = 2,2'-dihydroxy-1,1'-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 MS(n) experiments could be used to elucidate the redox behavior of the copper helicates.