Photoregulated ion-binding to azobenzene-linked ethylenediamines and iminodiacetic acids.
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概要
- 論文の詳細を見る
New photoresponsive complexones bearing two iminodiacetic acid units or ethylenediamine units at the two sides of an azobenzene through CH<SUB>2</SUB> or (CH<SUB>2</SUB>)<SUB>2</SUB> (AzoIDA(<I>n</I>=1,2) and AzoED(<I>n</I>=1,2), respectively) have been synthesized. The CH<SUB>2</SUB> and (CH<SUB>2</SUB>)<SUB>2</SUB> spacers were selected in order to examine the influence of the spacer length on the intramolecular cooperativity for the two ligands in the cis-isomers to coordinate to one metal ion. The thermal cis-to-trans isomerization of AzoIDA was efficiently suppressed by Zn(II) and Cu(II) while that of AzoED was suppressed only by Cu(II). The rate suppression supports the formation of the intramolecular chelate complexes with the metal ion. The measurements of ESR spectra of the cis-isomer·Cu(II) complexes indicated that the square-planar structure of the complexes is somewhat distorted and probably close to a lozenge. The stability constants (<I>K</I><SUB>s</SUB>) were determined by a displacement method. The <I>K</I><SUB>s</SUB> values for the cis-isomers were generally greater than those for the trans-isomers, and the <I>K</I><SUB>s</SUB> for <I>n</I>=2 series increased more clearly. In particular, the <I>K</I><SUB>s</SUB> for <I>cis</I>-AzoED(<I>n</I>=2)+Cu(II) was improved by 43.8 fold. The photoresponsive change in the stability constants suggests a possible application of the present system as light-driven ion pumps for heavy metal ions.
- 公益社団法人 日本化学会の論文
著者
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Shinkai Seiji
Department Of Applied Chemistry Faculty Of Engineering Kyushu University
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Iwamoto Masakazu
Department of industrial chemistry,Faculty of Engineering,Miyazaki,University
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MANABE Osamu
Department of Applied Chemistry, Faculty of Engineering, Nagasaki University
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NAKAMURA Shinichiro
Department of Gastroenterology & Hepatology, Okayama University Graduate School of Medicine and Dentistry, Okayama
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Nakashima Mikio
Department of Anesthesiology, Saga Medical School
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Nakashima Mikio
Department of Industrial Chemistry, Faculty of Engineering, Nagasaki University
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Nakamura Shinichiro
Department of Electronic Engineering, Graduate School of Engineering, Tohoku University
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