Theoretical and experimental investigation of the structural and spectroscopic properties of coumarin 343 fluoroionophores

Edith Botek, Philippe D'Antuono, Agnès Jacques, Raphaël Carion, Benoît Champagne, Laetitia Maton, Dorothée Taziaux, Jean Louis Habib-Jiwan

Research output: Contribution to journalArticle

Abstract

A joint theoretical-experimental investigation has been carried out to unravel the details of the complexation of cations by fluoroionophores based on coumarin 343 and to interpret the modifications in the ligand and also in the coumarin structural, electronic, magnetic, and vibrational properties. It is confirmed that C343-dea (1) complexes the cations by both the lactone and the amide oxygen atoms whereas for C343-crown (2) and C343-dibenzocrown (3), the cations are complexed by the oxygen atoms of the lactone as well as those of the crown ligand. These complexations induce geometric modifications, which are delocalized over the coumarin backbone and are related to electronic reorganizations that modify the spectroscopic signatures. This paper analyzes these signatures and shows how they are related as well as how they can be used to monitor the complexation process. Upon complexation, the UV-visible absorption spectra display a bathochromic shift of the most intense electronic transition; this shift is generally larger for the most flexible compound 1 as well as when complexing divalent cations. NMR spectra bear many signatures of the complexation, of which the most remarkable ones are the large shielding of C1 and the large deshieldings of C9 and C16. Additional makers of complexation are highlighted in the IR vibrational spectra, in particular the bands associated with the lactone and amide CO vibrations, which are downshifted when the corresponding CO is involved in the complexation mode and, otherwise, upshifted. A high degree of consistency characterizes the different geometrical, electronic, magnetic, and vibrational signatures, which substantiates the assignment of the modes of complexation in 1-3. In addition, the agreement between the experimental data and the theoretical values is rather satisfactory, in that it at least enables us to interpret the spectral signatures.

Original languageEnglish
Pages (from-to)14172-14187
Number of pages16
JournalPhysical Chemistry Chemical Physics
Volume12
Issue number42
DOIs
Publication statusPublished - 14 Nov 2010

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Complexation
signatures
cations
Lactones
electronics
Cations
amides
oxygen atoms
Carbon Monoxide
Amides
ligands
spectral signatures
magnetic signatures
shift
Oxygen
Ligands
bears
visible spectrum
Atoms
vibrational spectra

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title = "Theoretical and experimental investigation of the structural and spectroscopic properties of coumarin 343 fluoroionophores",
abstract = "A joint theoretical-experimental investigation has been carried out to unravel the details of the complexation of cations by fluoroionophores based on coumarin 343 and to interpret the modifications in the ligand and also in the coumarin structural, electronic, magnetic, and vibrational properties. It is confirmed that C343-dea (1) complexes the cations by both the lactone and the amide oxygen atoms whereas for C343-crown (2) and C343-dibenzocrown (3), the cations are complexed by the oxygen atoms of the lactone as well as those of the crown ligand. These complexations induce geometric modifications, which are delocalized over the coumarin backbone and are related to electronic reorganizations that modify the spectroscopic signatures. This paper analyzes these signatures and shows how they are related as well as how they can be used to monitor the complexation process. Upon complexation, the UV-visible absorption spectra display a bathochromic shift of the most intense electronic transition; this shift is generally larger for the most flexible compound 1 as well as when complexing divalent cations. NMR spectra bear many signatures of the complexation, of which the most remarkable ones are the large shielding of C1 and the large deshieldings of C9 and C16. Additional makers of complexation are highlighted in the IR vibrational spectra, in particular the bands associated with the lactone and amide CO vibrations, which are downshifted when the corresponding CO is involved in the complexation mode and, otherwise, upshifted. A high degree of consistency characterizes the different geometrical, electronic, magnetic, and vibrational signatures, which substantiates the assignment of the modes of complexation in 1-3. In addition, the agreement between the experimental data and the theoretical values is rather satisfactory, in that it at least enables us to interpret the spectral signatures.",
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Theoretical and experimental investigation of the structural and spectroscopic properties of coumarin 343 fluoroionophores. / Botek, Edith; D'Antuono, Philippe; Jacques, Agnès; Carion, Raphaël; Champagne, Benoît; Maton, Laetitia; Taziaux, Dorothée; Habib-Jiwan, Jean Louis.

In: Physical Chemistry Chemical Physics, Vol. 12, No. 42, 14.11.2010, p. 14172-14187.

Research output: Contribution to journalArticle

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AU - Habib-Jiwan, Jean Louis

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