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Issue 2, 2011
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Different metal-ion-induced dimeric self-assembling cavities based on thiacalix[4]benzocrown-4 isomers

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Abstract

To construct the self-assembly of metal-ion-induced well-ordered architectures based on calixcrowns, isomeric thiacalix[4]benzocrowns-4 1 and 2 with rigid and small crown units were employed as the new scaffolds. They all show remarkable selectivity for Ag+ and their complexation ability towards Ag+ results in two novel dimeric aggregates of calixcrowns, which were first evidenced by ESI-MS, 1H and DOSY-NMR spectra. Ultimately, X-ray diffraction experiments confirmed unambiguously the existence of the two metal-ion-induced dimers in lower rim/lower rim mode, and showed that dimerization of calixcrown 1 or 2 in the presence of Ag+ could form dimeric supramolecular cavity with a small inner room. Moreover, the positional isomerism of their crown units (o-benzocrown unit for ligand 1 and m-benzocrown unit for 2) led to a dramatic change in the configuration of the two dimeric cavities 1·Ag+ and 2·Ag+. For dimeric cavity 1·Ag+, two silver centers seamed two thiacalix[4]crown molecules together and resided at the edge of the dimeric self-assembling cavity; for dimeric cavity 2·Ag+, one Ag+ stitched two thiacalixcrowns together and was encapsulated in the center of the self-assembling cavity, while the other Ag+ is tied down to one end of the dimer. Consequently, as a result of the different construction of dimeric cavities 1·Ag+ and 2·Ag+ the extended structures of the complexes are also different. The neighbour self-assembling cavities 1·Ag+ are mutually oriented side-by-side and form a 1-D rectilineal polymeric chain. While, the neighbour self-assembling cavities 2·Ag+ arrange themselves in a typical head-to-tail fashion to form a zig-zag polymeric chain.

Graphical abstract: Different metal-ion-induced dimeric self-assembling cavities based on thiacalix[4]benzocrown-4 isomers

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Publication details

The article was received on 25 May 2010, accepted on 06 Oct 2010 and first published on 24 Nov 2010


Article type: Paper
DOI: 10.1039/C0DT00543F
Citation: Dalton Trans., 2011,40, 367-376
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    Different metal-ion-induced dimeric self-assembling cavities based on thiacalix[4]benzocrown-4 isomers

    X. Li, Y. Li, W. Yang, Y. Chen and S. Gong, Dalton Trans., 2011, 40, 367
    DOI: 10.1039/C0DT00543F

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