Proton transfer and supramolecular complex formation between Nile Blue and tetraundecylcalix[4]resorcinarene - A fluorescence spectroscopic study

M. Kubinyi, János Brátán, A. Grofcsik, L. Biczók, Benedek Poór, I. Bitter, A. Grün, Botond Bogáti, K. Tóth

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Abstract

The interactions between a calixarene host comprising dissociable protons, and an organic dye guest existing in a neutral base and in a protonated form, have been studied on model systems obtained by dissolving Nile Blue base (1) and tetraundecylcalix[4]resorcinarene (2) in two apolar solvents, dichloromethane and toluene. Steady state absorption and fluorescence spectroscopy and fluorescence lifetime measurements were applied as experimental methods. It has been established that the equilibrium composition of these systems is controlled predominantly by three reactions: (1) formation of the weakly bound complex 1·2; (2) simultaneous formation of the tightly bound ionic species with zero net charge 1+·2-(1+ = protonated form of 1,2- = monophenolate form of2); (3) protonation of the latter product in a subsequent step yielding 1+·2. The equilibrium constants for these reactions have been determined from the absorption spectra by an iterative procedure. The high value of the equilibrium constant for reaction (2) in toluene (9.8 × 106) is in accordance with the strongly solvatophobic nature of cation 1+ in this solvent. Thefluorescence lifetime of neutral base 1 increases whereas that of its protonated form, 1+, markedly decreases upon complexation. These effects have been interpreted in terms of intra- and intermolecular decay channels.

Original languageEnglish
Pages (from-to)1784-1789
Number of pages6
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number10
Publication statusPublished - 2002

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Proton transfer
Equilibrium constants
Toluene
Calixarenes
Fluorescence
Methylene Chloride
Protonation
Fluorescence spectroscopy
Complexation
Absorption spectroscopy
Cations
Protons
Absorption spectra
Coloring Agents
Chemical analysis
Nile Blue
resorcinarene

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Proton transfer and supramolecular complex formation between Nile Blue and tetraundecylcalix[4]resorcinarene - A fluorescence spectroscopic study",
abstract = "The interactions between a calixarene host comprising dissociable protons, and an organic dye guest existing in a neutral base and in a protonated form, have been studied on model systems obtained by dissolving Nile Blue base (1) and tetraundecylcalix[4]resorcinarene (2) in two apolar solvents, dichloromethane and toluene. Steady state absorption and fluorescence spectroscopy and fluorescence lifetime measurements were applied as experimental methods. It has been established that the equilibrium composition of these systems is controlled predominantly by three reactions: (1) formation of the weakly bound complex 1·2; (2) simultaneous formation of the tightly bound ionic species with zero net charge 1+·2-(1+ = protonated form of 1,2- = monophenolate form of2); (3) protonation of the latter product in a subsequent step yielding 1+·2. The equilibrium constants for these reactions have been determined from the absorption spectra by an iterative procedure. The high value of the equilibrium constant for reaction (2) in toluene (9.8 × 106) is in accordance with the strongly solvatophobic nature of cation 1+ in this solvent. Thefluorescence lifetime of neutral base 1 increases whereas that of its protonated form, 1+, markedly decreases upon complexation. These effects have been interpreted in terms of intra- and intermolecular decay channels.",
author = "M. Kubinyi and J{\'a}nos Br{\'a}t{\'a}n and A. Grofcsik and L. Bicz{\'o}k and Benedek Po{\'o}r and I. Bitter and A. Gr{\"u}n and Botond Bog{\'a}ti and K. T{\'o}th",
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T1 - Proton transfer and supramolecular complex formation between Nile Blue and tetraundecylcalix[4]resorcinarene - A fluorescence spectroscopic study

AU - Kubinyi, M.

AU - Brátán, János

AU - Grofcsik, A.

AU - Biczók, L.

AU - Poór, Benedek

AU - Bitter, I.

AU - Grün, A.

AU - Bogáti, Botond

AU - Tóth, K.

PY - 2002

Y1 - 2002

N2 - The interactions between a calixarene host comprising dissociable protons, and an organic dye guest existing in a neutral base and in a protonated form, have been studied on model systems obtained by dissolving Nile Blue base (1) and tetraundecylcalix[4]resorcinarene (2) in two apolar solvents, dichloromethane and toluene. Steady state absorption and fluorescence spectroscopy and fluorescence lifetime measurements were applied as experimental methods. It has been established that the equilibrium composition of these systems is controlled predominantly by three reactions: (1) formation of the weakly bound complex 1·2; (2) simultaneous formation of the tightly bound ionic species with zero net charge 1+·2-(1+ = protonated form of 1,2- = monophenolate form of2); (3) protonation of the latter product in a subsequent step yielding 1+·2. The equilibrium constants for these reactions have been determined from the absorption spectra by an iterative procedure. The high value of the equilibrium constant for reaction (2) in toluene (9.8 × 106) is in accordance with the strongly solvatophobic nature of cation 1+ in this solvent. Thefluorescence lifetime of neutral base 1 increases whereas that of its protonated form, 1+, markedly decreases upon complexation. These effects have been interpreted in terms of intra- and intermolecular decay channels.

AB - The interactions between a calixarene host comprising dissociable protons, and an organic dye guest existing in a neutral base and in a protonated form, have been studied on model systems obtained by dissolving Nile Blue base (1) and tetraundecylcalix[4]resorcinarene (2) in two apolar solvents, dichloromethane and toluene. Steady state absorption and fluorescence spectroscopy and fluorescence lifetime measurements were applied as experimental methods. It has been established that the equilibrium composition of these systems is controlled predominantly by three reactions: (1) formation of the weakly bound complex 1·2; (2) simultaneous formation of the tightly bound ionic species with zero net charge 1+·2-(1+ = protonated form of 1,2- = monophenolate form of2); (3) protonation of the latter product in a subsequent step yielding 1+·2. The equilibrium constants for these reactions have been determined from the absorption spectra by an iterative procedure. The high value of the equilibrium constant for reaction (2) in toluene (9.8 × 106) is in accordance with the strongly solvatophobic nature of cation 1+ in this solvent. Thefluorescence lifetime of neutral base 1 increases whereas that of its protonated form, 1+, markedly decreases upon complexation. These effects have been interpreted in terms of intra- and intermolecular decay channels.

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