Guest inclusion properties of calix[6]arene-based unimolecular cage compounds. On their high Cs+ and Ag+ selectivity and very slow metal exchange rates

Hideyuki Otsuka, Yoshio Suzuki, Atsushi Ikeda, Koji Araki, Seiji Shinkai

Research output: Contribution to journalArticlepeer-review

23 Citations (Scopus)

Abstract

The reaction of 1.3.5-tri-O-alkylated calix[6]arenes with 1,3,5- tris(bromomethyl)benzene yielded capped calix[6]arenes (2 with ten-butyl groups on the upper tim and 3 without tert-butyl groups) in unexpectedly high yields (80 - 91%). Combined studies of 2 and 3 by MM3 computation, X-ray analysis, and 1H NMR spectroscopy established that these calix[6]arenes feature a unique structure consisting of alternately-arranged three flattened mesitylene-linked phenyl units and three stand-up anisole units. Particularly, compound 2 possesses a closed ionophoric cavity: the upper hemisphere is closed by three ten-butyl groups of anisole units and the lower hemisphere is closed by a mesitylene cap and three anisole methoxy groups. The 1H NMR spectrum was scarcely changed at wide temperature range (30 ~ 130 °C), indicating that the structure is extremely rigidified. Both solvent extraction and spectroscopic studies established that this cavity shows the high selectivity toward Cs+ among alkali metal cations, the high affinity with Ag+, and the moderate affinity with RNH3+. Very surprisingly, the association-dissociation processes for 2 and cesium picrate was so slow that the rate could be followed by a conventional spectroscopic method. The thermodynamic parameters determined by kinetic studies disclosed that the major driving-force for Cs+ inclusion is the entropy term based on the desolvation.

Original languageEnglish
Pages (from-to)423-446
Number of pages24
JournalTetrahedron
Volume54
Issue number3-4
DOIs
Publication statusPublished - Jan 15 1998
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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