Molecular design of calixarenes. Part 3. Complexation thermodynamics of light lanthanoid nitrates with a novel p-tert-butylcalix[4]arene Schiff base in acetonitrile: An enhanced Eu3+ selectivity by side-arm ligation

Y. Liu, B. T. Zhao, H. Y. Zhang, T. Wada, Y. Inoue

研究成果: Article査読

26 被引用数 (Scopus)

抄録

A novel double-armed calix[4]arene derivative, 5,11,17,23-tetra-tert-butyl-25,27-bis{2-[N-(2-hydroxy-3-methoxy- benzylidene)amino]ethoxy}-26,28-dihydroxycalix[4]arene (3), has been synthesized by the reaction of 1,3-alternately lower-rim-modified bis(2-aminoethoxy)-substituted calix[4]arene (2) with o-vanillin in 90% yield. Calorimetric titrations have been performed in anhydrous acetonitrile at 25 °C to give the complex stability constant (Ks) and thermodynamic quantities for the complexation of light lanthanoid(III) nitrates (La-Gd) with 3. Using the present and reported data, the complexation behavior of the structurally related cyanomethyl analogue (1), aminoethyl analogue 2, and 3 is discussed comparatively from a thermodynamic point of view. Possessing donating vanillin side-arms and structural flexibility, 3 gave the highest Ks for Eu3+ among the light lanthanoid series. Having the same calix[4]arene skeleton in common, these hosts afforded distinctly different cation selectivity profiles. Thus, fairly low and invariant Ks values over the entire light lanthanoid series were obtained with the cyano analogue 1, while the incorporation of amino side-arms in 2 greatly enhanced the Ks for La3+ and less extensively for Ce3+ but no change was observed thereafter, giving a sharply declining pattern from La3+ to Pr3+ followed by a sudden leveling-off. In contrast, the vanillino analogue 3 showed a global enhancement of Ks for all light lanthanoids, displaying a unique selectivity profile with a broad peak at Nd31 and a sharp spike at Eu31. These results are accounted for in terms of the three-dimensional induced fit to lanthanoid ions by the lower-rim and side-arm donor atoms, which play a decisive role upon recognition of trivalent lanthanoid ions by the calix[4]arenes with flexible donating side-arms. Thermodynamically, the complexation is absolutely driven by the favorable enthalpy changes, but the cation selectivity is mainly determined by the less negative entropy changes.

本文言語English
ページ(範囲)1219-1223
ページ数5
ジャーナルJournal of the Chemical Society. Perkin Transactions 2
7
DOI
出版ステータスPublished - 2001
外部発表はい

ASJC Scopus subject areas

  • 化学 (全般)

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「Molecular design of calixarenes. Part 3. Complexation thermodynamics of light lanthanoid nitrates with a novel p-tert-butylcalix[4]arene Schiff base in acetonitrile: An enhanced Eu<sup>3+</sup> selectivity by side-arm ligation」の研究トピックを掘り下げます。これらがまとまってユニークなフィンガープリントを構成します。

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