Electrochemical and spectrophotometrical investigation of the electron-accepting strength of organic superelectrophiles: X-ray structure of their charge transfer complexes with tetrathiafulvalene

Guillaume Berionni, Anne Marie Gonalves, Charles Mathieu, Thomas Devic, Arnaud Etchéberry, Régis Goumont

Research output: Contribution to journalArticle

Abstract

Nitro Benzoxadiazoles (benzofurazans), benzoxadiazoles-N-oxide (benzofuroxans) and benzothiadiazoles are ranked amongst the strongest electrophiles known to date. In the past twenty years, their propensity to act as electron organic acceptors has been less studied. In this paper, we report on the study of their electrochemical behavior and on the structural characterization of charge transfer complexes (CTC) deriving from their interaction with tetrathiafulvalene (TTF) derivatives, both in solution and in the solid state. The first half wave reduction potentials (EI1/2) associated with a reversible monoelectronic transfer process of a large set of nitro substituted benzoxadiazoles (benzofurazans), benzoxadiazoles-N-oxide (benzofuroxans) and benzothiadiazoles have been determined through a detailed electrochemical approach in acetonitrile with a microelectrode network using the ferrocene as an internal reference potential in this electrochemical study. Determination of the electron affinity (EACT) of this series of substituted electrodeficient heteroaromatics as well as their LUMO energy was performed using the Charge Transfer Spectroscopic (CTS) method in solution and by DFT calculations, respectively. The use of the correlation EA CTversus the reversible half wave potential (EI1/2) appears to be a useful tool to estimate readily the EI1/2 or EACT values when they cannot be experimentally determined. The diffusion coefficient of these electrophiles has, for the first time, been determined in acetonitrile. These air stable electrodeficient heteroaromatics have been explored as potential new organic acceptors in the formation of charge transfer (CT) complexes with TTF derivatives. Crystallographic data of two CT complexes with TTF (especially the C-C and C-S bond lengths of the TTF moieties) indicate that these complexes exhibit weak electron delocalization and that both molecules remain neutral. Their resulting levels of charge transfer were probed using UV-visible, IR spectroscopy and by DFT calculations.

Original languageEnglish
Pages (from-to)2857-2869
Number of pages13
JournalPhysical Chemistry Chemical Physics
Volume13
Issue number7
DOIs
Publication statusPublished - 21 Feb 2011
Externally publishedYes

Fingerprint

Charge transfer
charge transfer
X rays
Electrons
electrons
x rays
Discrete Fourier transforms
Oxides
acetonitrile
Derivatives
Electron affinity
oxides
Microelectrodes
Bond length
electron affinity
Infrared spectroscopy
diffusion coefficient
tetrathiafulvalene
solid state
Molecules

Cite this

@article{7e6f9b924bcf445ea69f781914280612,
title = "Electrochemical and spectrophotometrical investigation of the electron-accepting strength of organic superelectrophiles: X-ray structure of their charge transfer complexes with tetrathiafulvalene",
abstract = "Nitro Benzoxadiazoles (benzofurazans), benzoxadiazoles-N-oxide (benzofuroxans) and benzothiadiazoles are ranked amongst the strongest electrophiles known to date. In the past twenty years, their propensity to act as electron organic acceptors has been less studied. In this paper, we report on the study of their electrochemical behavior and on the structural characterization of charge transfer complexes (CTC) deriving from their interaction with tetrathiafulvalene (TTF) derivatives, both in solution and in the solid state. The first half wave reduction potentials (EI1/2) associated with a reversible monoelectronic transfer process of a large set of nitro substituted benzoxadiazoles (benzofurazans), benzoxadiazoles-N-oxide (benzofuroxans) and benzothiadiazoles have been determined through a detailed electrochemical approach in acetonitrile with a microelectrode network using the ferrocene as an internal reference potential in this electrochemical study. Determination of the electron affinity (EACT) of this series of substituted electrodeficient heteroaromatics as well as their LUMO energy was performed using the Charge Transfer Spectroscopic (CTS) method in solution and by DFT calculations, respectively. The use of the correlation EA CTversus the reversible half wave potential (EI1/2) appears to be a useful tool to estimate readily the EI1/2 or EACT values when they cannot be experimentally determined. The diffusion coefficient of these electrophiles has, for the first time, been determined in acetonitrile. These air stable electrodeficient heteroaromatics have been explored as potential new organic acceptors in the formation of charge transfer (CT) complexes with TTF derivatives. Crystallographic data of two CT complexes with TTF (especially the C-C and C-S bond lengths of the TTF moieties) indicate that these complexes exhibit weak electron delocalization and that both molecules remain neutral. Their resulting levels of charge transfer were probed using UV-visible, IR spectroscopy and by DFT calculations.",
author = "Guillaume Berionni and Gonalves, {Anne Marie} and Charles Mathieu and Thomas Devic and Arnaud Etch{\'e}berry and R{\'e}gis Goumont",
year = "2011",
month = "2",
day = "21",
doi = "10.1039/c0cp01282c",
language = "English",
volume = "13",
pages = "2857--2869",
journal = "Physical chemistry chemical physics : PCCP",
issn = "1463-9076",
publisher = "Royal Society of Chemistry",
number = "7",

}

Electrochemical and spectrophotometrical investigation of the electron-accepting strength of organic superelectrophiles : X-ray structure of their charge transfer complexes with tetrathiafulvalene. / Berionni, Guillaume; Gonalves, Anne Marie; Mathieu, Charles; Devic, Thomas; Etchéberry, Arnaud; Goumont, Régis.

In: Physical Chemistry Chemical Physics, Vol. 13, No. 7, 21.02.2011, p. 2857-2869.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Electrochemical and spectrophotometrical investigation of the electron-accepting strength of organic superelectrophiles

T2 - X-ray structure of their charge transfer complexes with tetrathiafulvalene

AU - Berionni, Guillaume

AU - Gonalves, Anne Marie

AU - Mathieu, Charles

AU - Devic, Thomas

AU - Etchéberry, Arnaud

AU - Goumont, Régis

PY - 2011/2/21

Y1 - 2011/2/21

N2 - Nitro Benzoxadiazoles (benzofurazans), benzoxadiazoles-N-oxide (benzofuroxans) and benzothiadiazoles are ranked amongst the strongest electrophiles known to date. In the past twenty years, their propensity to act as electron organic acceptors has been less studied. In this paper, we report on the study of their electrochemical behavior and on the structural characterization of charge transfer complexes (CTC) deriving from their interaction with tetrathiafulvalene (TTF) derivatives, both in solution and in the solid state. The first half wave reduction potentials (EI1/2) associated with a reversible monoelectronic transfer process of a large set of nitro substituted benzoxadiazoles (benzofurazans), benzoxadiazoles-N-oxide (benzofuroxans) and benzothiadiazoles have been determined through a detailed electrochemical approach in acetonitrile with a microelectrode network using the ferrocene as an internal reference potential in this electrochemical study. Determination of the electron affinity (EACT) of this series of substituted electrodeficient heteroaromatics as well as their LUMO energy was performed using the Charge Transfer Spectroscopic (CTS) method in solution and by DFT calculations, respectively. The use of the correlation EA CTversus the reversible half wave potential (EI1/2) appears to be a useful tool to estimate readily the EI1/2 or EACT values when they cannot be experimentally determined. The diffusion coefficient of these electrophiles has, for the first time, been determined in acetonitrile. These air stable electrodeficient heteroaromatics have been explored as potential new organic acceptors in the formation of charge transfer (CT) complexes with TTF derivatives. Crystallographic data of two CT complexes with TTF (especially the C-C and C-S bond lengths of the TTF moieties) indicate that these complexes exhibit weak electron delocalization and that both molecules remain neutral. Their resulting levels of charge transfer were probed using UV-visible, IR spectroscopy and by DFT calculations.

AB - Nitro Benzoxadiazoles (benzofurazans), benzoxadiazoles-N-oxide (benzofuroxans) and benzothiadiazoles are ranked amongst the strongest electrophiles known to date. In the past twenty years, their propensity to act as electron organic acceptors has been less studied. In this paper, we report on the study of their electrochemical behavior and on the structural characterization of charge transfer complexes (CTC) deriving from their interaction with tetrathiafulvalene (TTF) derivatives, both in solution and in the solid state. The first half wave reduction potentials (EI1/2) associated with a reversible monoelectronic transfer process of a large set of nitro substituted benzoxadiazoles (benzofurazans), benzoxadiazoles-N-oxide (benzofuroxans) and benzothiadiazoles have been determined through a detailed electrochemical approach in acetonitrile with a microelectrode network using the ferrocene as an internal reference potential in this electrochemical study. Determination of the electron affinity (EACT) of this series of substituted electrodeficient heteroaromatics as well as their LUMO energy was performed using the Charge Transfer Spectroscopic (CTS) method in solution and by DFT calculations, respectively. The use of the correlation EA CTversus the reversible half wave potential (EI1/2) appears to be a useful tool to estimate readily the EI1/2 or EACT values when they cannot be experimentally determined. The diffusion coefficient of these electrophiles has, for the first time, been determined in acetonitrile. These air stable electrodeficient heteroaromatics have been explored as potential new organic acceptors in the formation of charge transfer (CT) complexes with TTF derivatives. Crystallographic data of two CT complexes with TTF (especially the C-C and C-S bond lengths of the TTF moieties) indicate that these complexes exhibit weak electron delocalization and that both molecules remain neutral. Their resulting levels of charge transfer were probed using UV-visible, IR spectroscopy and by DFT calculations.

UR - http://www.scopus.com/inward/record.url?scp=79551647700&partnerID=8YFLogxK

U2 - 10.1039/c0cp01282c

DO - 10.1039/c0cp01282c

M3 - Article

VL - 13

SP - 2857

EP - 2869

JO - Physical chemistry chemical physics : PCCP

JF - Physical chemistry chemical physics : PCCP

SN - 1463-9076

IS - 7

ER -