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

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

Izvornik
Journal of the American Chemical Society (0002-7863) 136 (2014), 33; 11830-11838

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
trinuclear helicates; diastereoselective self-assembly; X-ray diffraction; redox chemistry

Sažetak
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 MSn experiments could be used to elucidate the redox behavior of the copper helicates.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA