Reactive pseudorotaxanes: Inclusion complexation of reduced viologens by the hosts β-cyclodextrin and heptakis(2,6-di-O-methyl)-β-cyclodextrin

Armen Mirzoian, Angel Kaifer

Research output: Contribution to journalArticle

143 Citations (Scopus)

Abstract

The complexation of three guests containing 4,4'-bipyridinium redox-active residues by β-cyclodextrin (β-CD) and its heptakis-(2,6-O-dimethyl) analogue (DM-β-CD) was investigated by means of voltammetric techniques. The three 4,4'-bipyridinium (viologen) derivatives used as guests were designed to be water-soluble in all three accessible oxidation states. The N-substituents chosen to enhance aqueous solubility were: 2-(2-(2-ethoxy)ethoxy)ethanol (guest 12+), 6-hexanoate (guest 2), and 3-propanesulfonate (guest 3). Detailed analysis of the voltammetric results by digital simulation techniques revealed that the oxidized forms of the guests did not interact appreciably with either CD host; the two-electron reduced guests formed extremely stable inclusion complexes, with association constants in the range 103 - 104 M-1, while the cation radical forms exhibited intermediate binding affinities (≃102 M-1). In all cases, DM-β-CD was found to form more stable complexes than unmodified β-CD.

Original languageEnglish
Pages (from-to)1052-1058
Number of pages7
JournalChemistry - A European Journal
Volume3
Issue number7
StatePublished - Jul 1 1997

Fingerprint

Viologens
Rotaxanes
Cyclodextrins
Complexation
Cations
Ethanol
Solubility
Positive ions
Association reactions
Derivatives
Oxidation
Electrons
Water
hexanoic acid
propylsulfonic acid
Oxidation-Reduction

Keywords

  • Cyclic voltammetry
  • Cyclodextrins
  • Host-guest chemistry
  • Pseudorotaxanes
  • Viologens

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Reactive pseudorotaxanes: Inclusion complexation of reduced viologens by the hosts β-cyclodextrin and heptakis(2,6-di-O-methyl)-β-cyclodextrin",
abstract = "The complexation of three guests containing 4,4'-bipyridinium redox-active residues by β-cyclodextrin (β-CD) and its heptakis-(2,6-O-dimethyl) analogue (DM-β-CD) was investigated by means of voltammetric techniques. The three 4,4'-bipyridinium (viologen) derivatives used as guests were designed to be water-soluble in all three accessible oxidation states. The N-substituents chosen to enhance aqueous solubility were: 2-(2-(2-ethoxy)ethoxy)ethanol (guest 12+), 6-hexanoate (guest 2), and 3-propanesulfonate (guest 3). Detailed analysis of the voltammetric results by digital simulation techniques revealed that the oxidized forms of the guests did not interact appreciably with either CD host; the two-electron reduced guests formed extremely stable inclusion complexes, with association constants in the range 103 - 104 M-1, while the cation radical forms exhibited intermediate binding affinities (≃102 M-1). In all cases, DM-β-CD was found to form more stable complexes than unmodified β-CD.",
keywords = "Cyclic voltammetry, Cyclodextrins, Host-guest chemistry, Pseudorotaxanes, Viologens",
author = "Armen Mirzoian and Angel Kaifer",
year = "1997",
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T2 - Inclusion complexation of reduced viologens by the hosts β-cyclodextrin and heptakis(2,6-di-O-methyl)-β-cyclodextrin

AU - Mirzoian, Armen

AU - Kaifer, Angel

PY - 1997/7/1

Y1 - 1997/7/1

N2 - The complexation of three guests containing 4,4'-bipyridinium redox-active residues by β-cyclodextrin (β-CD) and its heptakis-(2,6-O-dimethyl) analogue (DM-β-CD) was investigated by means of voltammetric techniques. The three 4,4'-bipyridinium (viologen) derivatives used as guests were designed to be water-soluble in all three accessible oxidation states. The N-substituents chosen to enhance aqueous solubility were: 2-(2-(2-ethoxy)ethoxy)ethanol (guest 12+), 6-hexanoate (guest 2), and 3-propanesulfonate (guest 3). Detailed analysis of the voltammetric results by digital simulation techniques revealed that the oxidized forms of the guests did not interact appreciably with either CD host; the two-electron reduced guests formed extremely stable inclusion complexes, with association constants in the range 103 - 104 M-1, while the cation radical forms exhibited intermediate binding affinities (≃102 M-1). In all cases, DM-β-CD was found to form more stable complexes than unmodified β-CD.

AB - The complexation of three guests containing 4,4'-bipyridinium redox-active residues by β-cyclodextrin (β-CD) and its heptakis-(2,6-O-dimethyl) analogue (DM-β-CD) was investigated by means of voltammetric techniques. The three 4,4'-bipyridinium (viologen) derivatives used as guests were designed to be water-soluble in all three accessible oxidation states. The N-substituents chosen to enhance aqueous solubility were: 2-(2-(2-ethoxy)ethoxy)ethanol (guest 12+), 6-hexanoate (guest 2), and 3-propanesulfonate (guest 3). Detailed analysis of the voltammetric results by digital simulation techniques revealed that the oxidized forms of the guests did not interact appreciably with either CD host; the two-electron reduced guests formed extremely stable inclusion complexes, with association constants in the range 103 - 104 M-1, while the cation radical forms exhibited intermediate binding affinities (≃102 M-1). In all cases, DM-β-CD was found to form more stable complexes than unmodified β-CD.

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KW - Viologens

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