201657-71-8Relevant academic research and scientific papers
Constitutionally asymmetric and chiral [2]pseudorotaxanes
Asakawa, Masumi,Ashton, Peter R.,Hayes, Wayne,Janssen, Henk M.,Meijer,Menzer, Stephan,Pasini, Dario,Stoddart, J. Fraser,White, Andrew J. P.,Williams, David J.
, p. 920 - 931 (2007/10/03)
The self-assembly and characterization of a range of chiral pseudorotaxanes has been explored using chiroptical methods. The syntheses of (i) constitutionally asymmetric acyclic hydroquinone-containing polyethers and (ii) optically active hydroquinone-containing acyclic polyethers, bearing pairs of methyl or isobutyl groups related to each other in a C2-symmetric manner within the polyether backbone, are described. The combination of (i) the tetracationic cyclophane cyclobis(paraquat-p-phenylene) tetrakis(hexafluorophosphate), possessing a π-electron deficient cavity, and (ii) the linear noncentrosymmetric acyclic polyethers produces [2]pseudorotaxanes that have been characterized by 1H NMR, UV/vis and circular dichroism (CD) spectroscopies in solution and by X-ray crystallography in the solid state. The introduction of constitutional asymmetry or chirality gives rise to a number of different geometries for the [2]pseudorotaxanes in both the solution and solid states. In particular, CD-spectroscopic measurements on the optically active [2]pseudorotaxanes have shown that-depending on the positions of the C2 symmetrically related chiral centers in the polyether chains with respect to the hydroquinone rings - the chirality present in the π-electron rich threadlike guest can induce chirality that is associated with the supramolecular structure as a whole, resulting in a chiral charge-transfer transition involving not only the π-donors in the chiral guests but also the π-acceptors in the achiral host.
