Molecular Design of Tetraazamacrocyclic Derivatives Bearing a Spirobenzopyran and Three Carboxymethyl Moieties and Their Metal-Ion Complexing Behavior

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Tetraazacyclododecane and tetraazacyclotetradecane derivatives bearing a spirobenzopyran and three carboxymethyl moieties, <b>1</b> and <b>2</b>, and a diethylenetriamine derivative bearing a spirobenzopyran and four carboxymethyl moieties <b>3</b> were synthesized. The isomerization behaviors based on the spirobenzopyran moiety of these ligands were studied by UV-visible spectrophotometry in aqueous solutions containing various metal ions at neutral pH. These ligands formed stable 1:1 complexes with lanthanide ions, while the spirobenzopyran moiety was isomerized to its corresponding merocyanine form even under dark conditions. In aqueous solutions containing a lanthanide ion, the absorption spectra of <b>1</b> or <b>2</b> showed remarkable blue shifts, while absorbances at the maximum absorption wavelengths in the visible region were enhanced; such changes are attributable to the isomerization to the merocyanine form of the spirobenzopyran moiety. These results suggest that the phenolate anion of the merocyanine moiety interacts very strongly with a lanthanide ion bound by the complexing moiety because of the high charge density of lanthanide ions. In contrast, the absorbance of merocyanine form was decreased by the complexation of the macrocyclic ligand with transition metal ions, such as Cu<sup>2+</sup> and Zn<sup>2+</sup>. This result indicates that macrocyclic ligands, <b>1</b> and <b>2</b>, formed complexes with transition metal ions only by the aminocarboxylate moieties, and the phenolate ion of merocyanine moiety was not able to participate in the complexation. This conclusion was also demonstrated by density functional theory calculations.

収録刊行物

  • Analytical sciences : the international journal of the Japan Society for Analytical Chemistry  

    Analytical sciences : the international journal of the Japan Society for Analytical Chemistry 24(4), 463-469, 2008-04-10 

    The Japan Society for Analytical Chemistry

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各種コード

  • NII論文ID(NAID)
    10021099500
  • NII書誌ID(NCID)
    AA10500785
  • 本文言語コード
    ENG
  • 資料種別
    ART
  • ISSN
    09106340
  • NDL 記事登録ID
    9452062
  • NDL 雑誌分類
    ZP4(科学技術--化学・化学工業--分析化学)
  • NDL 請求記号
    Z54-F482
  • データ提供元
    CJP書誌  NDL  J-STAGE 
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