title: Enantiomerically pure trinuclear helicates via diastereoselective self-assembly and characterization of their redox chemistry.
abstract: 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.
authors: Kekulé-Institute of Organic Chemistry and Biochemistry, University of Bonn , Gerhard-Domagk-Str. 1, D-53121 Bonn, Germany.
authors: Christoph
authors: C
authors: Gütz
authors: Rainer
authors: R
authors: Hovorka
authors: Niklas
authors: N
authors: Struch
authors: Jens
authors: J
authors: Bunzen
authors: Georg
authors: G
authors: Meyer-Eppler
authors: Zheng-Wang
authors: ZW
authors: Qu
authors: Stefan
authors: S
authors: Grimme
authors: Filip
authors: F
authors: Topić
authors: Kari
authors: K
authors: Rissanen
authors: Mario
authors: M
authors: Cetina
authors: Marianne
authors: M
authors: Engeser
authors: Arne
authors: A
authors: Lützen