Constitutionally asymmetric and chiral [2]pseudorotaxanes

被引:46
作者
Asakawa, M
Ashton, PR
Hayes, W
Janssen, HM
Meijer, EW
Menzer, S
Pasini, D
Stoddart, JF
White, AJP
Williams, DJ
机构
[1] Eindhoven Univ Technol, Organ Chem Lab, NL-5600 MB Eindhoven, Netherlands
[2] Univ Birmingham, Sch Chem, Birmingham B15 2TT, W Midlands, England
[3] Univ London Imperial Coll Sci Technol & Med, Dept Chem, London SW7 2AY, England
关键词
D O I
10.1021/ja970018i
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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 C-2-symmetric manner within the polyether backbone, are described. The combination of (i) the tetracationic cyclophane cyclobis(paraquat-p-phenylene) tetrakis(hexafluorophosphate), possessing a pi-electron deficient cavity, and (ii) the linear noncentrosymmetric acyclic polyethers produces [2]pseudorotaxanes that have been characterized by H-1 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 C-2 symmetrically related chiral centers in the polyether chains with respect to the hydroquinone rings-the chirality present in the pi-electron rich threadrike 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 pi-donors in the chiral guests but also the pi-acceptors in the achiral host.
引用
收藏
页码:920 / 931
页数:12
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