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

研究成果: ジャーナルへの寄稿記事

23 引用 (Scopus)

抄録

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.

元の言語英語
ページ(範囲)423-446
ページ数24
ジャーナルTetrahedron
54
発行部数3-4
DOI
出版物ステータス出版済み - 1 15 1998
外部発表Yes

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Metals
Alkali Metals
Cesium
X ray analysis
Entropy
Solvent extraction
Benzene
Thermodynamics
Nuclear magnetic resonance spectroscopy
Cations
Magnetic Resonance Spectroscopy
Nuclear magnetic resonance
X-Rays
Association reactions
Kinetics
Temperature
calix(6)arene
anisole
mesitylene
Proton Magnetic Resonance Spectroscopy

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

これを引用

Guest inclusion properties of calix[6]arene-based unimolecular cage compounds. On their high Cs+ and Ag+ selectivity and very slow metal exchange rates. / Otsuka, Hideyuki; Suzuki, Yoshio; Ikeda, Atsushi; Araki, Koji; Shinkai, Seiji.

:: Tetrahedron, 巻 54, 番号 3-4, 15.01.1998, p. 423-446.

研究成果: ジャーナルへの寄稿記事

Otsuka, Hideyuki ; Suzuki, Yoshio ; Ikeda, Atsushi ; Araki, Koji ; Shinkai, Seiji. / Guest inclusion properties of calix[6]arene-based unimolecular cage compounds. On their high Cs+ and Ag+ selectivity and very slow metal exchange rates. :: Tetrahedron. 1998 ; 巻 54, 番号 3-4. pp. 423-446.
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