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

摘要

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 D_(2~-) symmeteric double-stranded trinuclear helicates upon coordination to copper(Ⅰ) and silver(Ⅰ) ions and to D_3-symmetric triple-stranded trinuclear helicates upon coordination to copper(Ⅱ), zinc(n), 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″ experiments could be used to elucidate the redox behavior of the copper helicates.