水溶液中阴离子与与全-O-甲基化β-环糊精络合的铁卟啉的结合。
Anion binding to a ferric porphyrin complexed with per-O-methylated beta-cyclodextrin in aqueous solution.
作者信息
Kano Koji, Kitagishi Hiroaki, Tamura Shigeto, Yamada Akihisa
机构信息
Department of Molecular Science and Technology, Faculty of Engineering, Doshisha University, Kyotanabe, Kyoto 610-0321, Japan.
出版信息
J Am Chem Soc. 2004 Nov 24;126(46):15202-10. doi: 10.1021/ja045472i.
5,10,15,20-Tetrakis(4-sulfonatophenyl)porphinato iron(III) (Fe(III)TPPS) forms a very stable 1:2 complex with heptakis(2,3,6-tri-O-methyl)-beta-cyclodextrin (TMe-beta-CD), whose iron(III) center is located at a hydrophobic cleft formed by two face-to-face TMe-beta-CD molecules. Various inorganic anions (X(-)) such as F(-), Cl(-), Br(-), I(-), N(3)(-), and SCN(-) coordinate to Fe(III)TPPS(TMe-beta-CD)(2) to form five-coordinate high-spin Fe(III)TPPS(X)(TMe-beta-CD)(2), while no coordination occurs with ClO(4)(-), H(2)PO(4)(-), NO(3)(-), and HSO(4)(-). Except for F(-), none of the anions investigated coordinate to Fe(III)TPPS in the absence of TMe-beta-CD due to extensive hydration to the anions as well as to Fe(III)TPPS. The present system shows a high selectivity toward the N(3)(-) anion. The thermodynamics suggests that Lewis basicity, hydrophilicity, and shape of an X(-) anion are the main factors to determine the stability of the Fe(III)TPPS(X)(TMe-beta-CD)(2) complex.
5,10,15,20-四（4-磺酸苯基）卟吩铁（III）（Fe（III）TPPS）与七（2,3,6-三-O-甲基）-β-环糊精（TMe-β-CD）形成非常稳定的1:2配合物，其铁（III）中心位于由两个面对面的TMe-β-CD分子形成的疏水裂缝中。各种无机阴离子（X（-）），如F（-）、Cl（-）、Br（-）、I（-）、N₃（-）和SCN（-）与Fe（III）TPPS（TMe-β-CD）₂配位形成五配位高自旋Fe（III）TPPS（X）（TMe-β-CD）₂，而与ClO₄（-）、H₂PO₄（-）、NO₃（-）和HSO₄（-）不发生配位。除F（-）外，由于阴离子以及Fe（III）TPPS的广泛水合作用，在没有TMe-β-CD的情况下，所研究的阴离子均不与Fe（III）TPPS配位。本体系对N₃（-）阴离子表现出高选择性。热力学表明，X（-）阴离子的路易斯碱性、亲水性和形状是决定Fe（III）TPPS（X）（TMe-β-CD）₂配合物稳定性的主要因素。
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