Azaparacyclophanes with metal-binding sites. Part 1. Preparation, characterization, and molecular recognition behaviour of hexapus azaparacyclophane and its iron(III) complex

Yoshio Hisaeda, Takeshi Ihara, Teruhisa Ohno, Yukito Murakami, Yonezo Maeda

研究成果: ジャーナルへの寄稿記事

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All the catechol moieties of a hexapus triaza[3.3.3]paracyclophane having three catechol moieties and six hydrocarbon chains (1) undergo coordination interactions with the iron(III) ion in a 1:1 molar ratio of 1 to iron(III) above pH 6 in an aqueous medium. Two different iron(III) complexes of 1, A and B in a 1:1 molar ratio, are in the high spin iron(in) state as characterized by electronic, EPR and Mössbauer spectroscopy: A is a hexacoordinated mononuclear complex with half-protonated catecholato groups, subjected to considerable structural distortion; B is a hexa-coordinated mononuclear complex with complete dissociation of all the catechol protons, retaining high structural symmetry. The molecular recognition behaviour of 1 and Fe-complex A toward hydrophobic guest molecules has been investigated in aqueous HEPES and acetate buffers at 30.0 °C and μ 0.10 mol dm-3. The hexapus cyclophane 1 recognizes organic guests through hydrophobic and electrostatic interactions; anionic and non-ionic guests, 7-hydroxy-8-phenylazonaphthalene-1, 3-disulfonate (OG) and 2-hydroxy-1-(2-pyridylazo)naphthalene (PAN), respectively, are incorporated into host 1 with binding constants of the order of 105 dm3 mol-1, while a cationic guest, 2-(p-dimethylaminostyryl)-1-ethylquinolinium (QR), is not included in the host. The guest-binding behaviour of Fe-complex A toward OG and PAN is much enhanced relative to that of 1 as effected by hydrophobic, electrostatic and coordination interactions under conditions identical to those applied to 1; the binding constant for OG is nearly pH-independent in a pH range of 3-8, while that for PAN is pH-dependent because the coordination interaction with the host is subject to change by pH.

元の言語英語
ページ(範囲)595-604
ページ数10
ジャーナルJournal of the Chemical Society, Perkin Transactions 2
発行部数4
出版物ステータス出版済み - 12 1 1992

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Molecular recognition
Iron
Metals
Binding Sites
HEPES
Hydrocarbons
Coulomb interactions
Paramagnetic resonance
Protons
Electrostatics
Buffers

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

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title = "Azaparacyclophanes with metal-binding sites. Part 1. Preparation, characterization, and molecular recognition behaviour of hexapus azaparacyclophane and its iron(III) complex",
abstract = "All the catechol moieties of a hexapus triaza[3.3.3]paracyclophane having three catechol moieties and six hydrocarbon chains (1) undergo coordination interactions with the iron(III) ion in a 1:1 molar ratio of 1 to iron(III) above pH 6 in an aqueous medium. Two different iron(III) complexes of 1, A and B in a 1:1 molar ratio, are in the high spin iron(in) state as characterized by electronic, EPR and M{\"o}ssbauer spectroscopy: A is a hexacoordinated mononuclear complex with half-protonated catecholato groups, subjected to considerable structural distortion; B is a hexa-coordinated mononuclear complex with complete dissociation of all the catechol protons, retaining high structural symmetry. The molecular recognition behaviour of 1 and Fe-complex A toward hydrophobic guest molecules has been investigated in aqueous HEPES and acetate buffers at 30.0 °C and μ 0.10 mol dm-3. The hexapus cyclophane 1 recognizes organic guests through hydrophobic and electrostatic interactions; anionic and non-ionic guests, 7-hydroxy-8-phenylazonaphthalene-1, 3-disulfonate (OG) and 2-hydroxy-1-(2-pyridylazo)naphthalene (PAN), respectively, are incorporated into host 1 with binding constants of the order of 105 dm3 mol-1, while a cationic guest, 2-(p-dimethylaminostyryl)-1-ethylquinolinium (QR), is not included in the host. The guest-binding behaviour of Fe-complex A toward OG and PAN is much enhanced relative to that of 1 as effected by hydrophobic, electrostatic and coordination interactions under conditions identical to those applied to 1; the binding constant for OG is nearly pH-independent in a pH range of 3-8, while that for PAN is pH-dependent because the coordination interaction with the host is subject to change by pH.",
author = "Yoshio Hisaeda and Takeshi Ihara and Teruhisa Ohno and Yukito Murakami and Yonezo Maeda",
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T1 - Azaparacyclophanes with metal-binding sites. Part 1. Preparation, characterization, and molecular recognition behaviour of hexapus azaparacyclophane and its iron(III) complex

AU - Hisaeda, Yoshio

AU - Ihara, Takeshi

AU - Ohno, Teruhisa

AU - Murakami, Yukito

AU - Maeda, Yonezo

PY - 1992/12/1

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N2 - All the catechol moieties of a hexapus triaza[3.3.3]paracyclophane having three catechol moieties and six hydrocarbon chains (1) undergo coordination interactions with the iron(III) ion in a 1:1 molar ratio of 1 to iron(III) above pH 6 in an aqueous medium. Two different iron(III) complexes of 1, A and B in a 1:1 molar ratio, are in the high spin iron(in) state as characterized by electronic, EPR and Mössbauer spectroscopy: A is a hexacoordinated mononuclear complex with half-protonated catecholato groups, subjected to considerable structural distortion; B is a hexa-coordinated mononuclear complex with complete dissociation of all the catechol protons, retaining high structural symmetry. The molecular recognition behaviour of 1 and Fe-complex A toward hydrophobic guest molecules has been investigated in aqueous HEPES and acetate buffers at 30.0 °C and μ 0.10 mol dm-3. The hexapus cyclophane 1 recognizes organic guests through hydrophobic and electrostatic interactions; anionic and non-ionic guests, 7-hydroxy-8-phenylazonaphthalene-1, 3-disulfonate (OG) and 2-hydroxy-1-(2-pyridylazo)naphthalene (PAN), respectively, are incorporated into host 1 with binding constants of the order of 105 dm3 mol-1, while a cationic guest, 2-(p-dimethylaminostyryl)-1-ethylquinolinium (QR), is not included in the host. The guest-binding behaviour of Fe-complex A toward OG and PAN is much enhanced relative to that of 1 as effected by hydrophobic, electrostatic and coordination interactions under conditions identical to those applied to 1; the binding constant for OG is nearly pH-independent in a pH range of 3-8, while that for PAN is pH-dependent because the coordination interaction with the host is subject to change by pH.

AB - All the catechol moieties of a hexapus triaza[3.3.3]paracyclophane having three catechol moieties and six hydrocarbon chains (1) undergo coordination interactions with the iron(III) ion in a 1:1 molar ratio of 1 to iron(III) above pH 6 in an aqueous medium. Two different iron(III) complexes of 1, A and B in a 1:1 molar ratio, are in the high spin iron(in) state as characterized by electronic, EPR and Mössbauer spectroscopy: A is a hexacoordinated mononuclear complex with half-protonated catecholato groups, subjected to considerable structural distortion; B is a hexa-coordinated mononuclear complex with complete dissociation of all the catechol protons, retaining high structural symmetry. The molecular recognition behaviour of 1 and Fe-complex A toward hydrophobic guest molecules has been investigated in aqueous HEPES and acetate buffers at 30.0 °C and μ 0.10 mol dm-3. The hexapus cyclophane 1 recognizes organic guests through hydrophobic and electrostatic interactions; anionic and non-ionic guests, 7-hydroxy-8-phenylazonaphthalene-1, 3-disulfonate (OG) and 2-hydroxy-1-(2-pyridylazo)naphthalene (PAN), respectively, are incorporated into host 1 with binding constants of the order of 105 dm3 mol-1, while a cationic guest, 2-(p-dimethylaminostyryl)-1-ethylquinolinium (QR), is not included in the host. The guest-binding behaviour of Fe-complex A toward OG and PAN is much enhanced relative to that of 1 as effected by hydrophobic, electrostatic and coordination interactions under conditions identical to those applied to 1; the binding constant for OG is nearly pH-independent in a pH range of 3-8, while that for PAN is pH-dependent because the coordination interaction with the host is subject to change by pH.

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