Benzothioxanthene Dicarboximide as a Tuneable Electrogenerated Chemiluminescence Dye

Alice L. Dauphin; José María Andrés Castán; Jing Yu; Philippe Blanchard; Neso Sojic; Hyun S. Ahn; Bright Walker; Clément Cabanetos; Laurent Bouffier

doi:10.1002/celc.202200967

Benzothioxanthene Dicarboximide as a Tuneable Electrogenerated Chemiluminescence Dye

Alice L. Dauphin, José María Andrés Castán, Jing Yu, Philippe Blanchard, Neso Sojic, Hyun S. Ahn, Bright Walker, Clément Cabanetos, Laurent Bouffier

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Overlooked for years, the promising benzothioxanthene dicarboximide (BTXI) structure is nonetheless known to be an excellent fluorophore. As a further step towards the exploration of this rylene structure, the generation of electrochemiluminescence (ECL) in acetonitrile solutions is investigated herein as well as its direct comparison with a diphenylamine (DPA) derivative. Electrochemical characterization shows that the bare BTXI can be reversibly reduced or oxidized, characteristics which suggest the possibility that the electrogenerated reactive species can be exploited in the context of ECL. As a result, the BTXI moiety was found to be ECL-active in both annihilation and co-reactant mechanisms. Tri-n-propylamine (TPA) and benzoyl peroxide (BPO) were selected as sacrificial co-reactants for promoting ECL. An ECL efficiency of 13 % (BTXI) and 6 % (BTXI-DPA) compared to that of Ru(bpy)₃²⁺ was found when using TPA in oxidative ECL. Moreover, the ECL efficiency increased to 75 % and 55 % of Ru(bpy)₃²⁺ with BPO (i. e. reductive-oxidation ECL) for BTXI and BTXI-DPA, respectively. These results can be understood by calculating the free enthalpy of the redox reactions associated with each ECL pathway. Although the BTXI-DPA red emitter exhibits more suitable thermodynamic properties, the BTXI green emitter is nonetheless more effective in combination with a co-reactant due to a much larger photoluminescence quantum yield. The ECL spectra of the two molecules are compared to their photoluminescence spectra, revealing the involvement of the same excited states in the two different photoemission processes. In turn, the chemical engineering of BTXI is shown to be an effective platform for achieving tuneable ECL generation.

Original language	English
Article number	e202200967
Journal	ChemElectroChem
Volume	9
Issue number	24
DOIs	https://doi.org/10.1002/celc.202200967
Publication status	Published - 2022 Dec 27

Bibliographical note

Funding Information:
A. L. D. acknowledges the University of Bordeaux for a PhD studentship. L. B. thanks the CNRS and the Department Science & Technology of the University of Bordeaux for funding (AAP 2017, project MICRO-REDOX). J. M. A. C. thanks the European Union's Horizon 2020 research and innovation program under Marie Sklodowska-Curie Grant agreement No. 722651 (SEPOMO). C. C. thanks the ANR for the funding of the “BTXI-APOGEE” project (ANR-20-CE05-0029). N. S. thanks the Eurorégion Nouvelle-Aquitaine Euskadi Navarre for funding the ECLICARE project.

Funding Information:
A. L. D. acknowledges the University of Bordeaux for a PhD studentship. L. B. thanks the CNRS and the Department Science & Technology of the University of Bordeaux for funding (AAP 2017, project MICRO‐REDOX). J. M. A. C. thanks the European Union's Horizon 2020 research and innovation program under Marie Sklodowska‐Curie Grant agreement No. 722651 (SEPOMO). C. C. thanks the ANR for the funding of the “BTXI‐APOGEE” project (ANR‐20‐CE05‐0029). N. S. thanks the Eurorégion Nouvelle‐Aquitaine Euskadi Navarre for funding the ECLICARE project.

Publisher Copyright:
© 2022 Wiley-VCH GmbH.

All Science Journal Classification (ASJC) codes

Catalysis
Electrochemistry

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10.1002/celc.202200967

Cite this

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title = "Benzothioxanthene Dicarboximide as a Tuneable Electrogenerated Chemiluminescence Dye",

abstract = "Overlooked for years, the promising benzothioxanthene dicarboximide (BTXI) structure is nonetheless known to be an excellent fluorophore. As a further step towards the exploration of this rylene structure, the generation of electrochemiluminescence (ECL) in acetonitrile solutions is investigated herein as well as its direct comparison with a diphenylamine (DPA) derivative. Electrochemical characterization shows that the bare BTXI can be reversibly reduced or oxidized, characteristics which suggest the possibility that the electrogenerated reactive species can be exploited in the context of ECL. As a result, the BTXI moiety was found to be ECL-active in both annihilation and co-reactant mechanisms. Tri-n-propylamine (TPA) and benzoyl peroxide (BPO) were selected as sacrificial co-reactants for promoting ECL. An ECL efficiency of 13 % (BTXI) and 6 % (BTXI-DPA) compared to that of Ru(bpy)32+ was found when using TPA in oxidative ECL. Moreover, the ECL efficiency increased to 75 % and 55 % of Ru(bpy)32+ with BPO (i. e. reductive-oxidation ECL) for BTXI and BTXI-DPA, respectively. These results can be understood by calculating the free enthalpy of the redox reactions associated with each ECL pathway. Although the BTXI-DPA red emitter exhibits more suitable thermodynamic properties, the BTXI green emitter is nonetheless more effective in combination with a co-reactant due to a much larger photoluminescence quantum yield. The ECL spectra of the two molecules are compared to their photoluminescence spectra, revealing the involvement of the same excited states in the two different photoemission processes. In turn, the chemical engineering of BTXI is shown to be an effective platform for achieving tuneable ECL generation.",

author = "Dauphin, {Alice L.} and {Andr{\'e}s Cast{\'a}n}, {Jos{\'e} Mar{\'i}a} and Jing Yu and Philippe Blanchard and Neso Sojic and Ahn, {Hyun S.} and Bright Walker and Cl{\'e}ment Cabanetos and Laurent Bouffier",

note = "Funding Information: A. L. D. acknowledges the University of Bordeaux for a PhD studentship. L. B. thanks the CNRS and the Department Science & Technology of the University of Bordeaux for funding (AAP 2017, project MICRO-REDOX). J. M. A. C. thanks the European Union's Horizon 2020 research and innovation program under Marie Sklodowska-Curie Grant agreement No. 722651 (SEPOMO). C. C. thanks the ANR for the funding of the “BTXI-APOGEE” project (ANR-20-CE05-0029). N. S. thanks the Euror{\'e}gion Nouvelle-Aquitaine Euskadi Navarre for funding the ECLICARE project. Funding Information: A. L. D. acknowledges the University of Bordeaux for a PhD studentship. L. B. thanks the CNRS and the Department Science & Technology of the University of Bordeaux for funding (AAP 2017, project MICRO‐REDOX). J. M. A. C. thanks the European Union's Horizon 2020 research and innovation program under Marie Sklodowska‐Curie Grant agreement No. 722651 (SEPOMO). C. C. thanks the ANR for the funding of the “BTXI‐APOGEE” project (ANR‐20‐CE05‐0029). N. S. thanks the Euror{\'e}gion Nouvelle‐Aquitaine Euskadi Navarre for funding the ECLICARE project. Publisher Copyright: {\textcopyright} 2022 Wiley-VCH GmbH.",

year = "2022",

month = dec,

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doi = "10.1002/celc.202200967",

language = "English",

volume = "9",

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T1 - Benzothioxanthene Dicarboximide as a Tuneable Electrogenerated Chemiluminescence Dye

AU - Dauphin, Alice L.

AU - Andrés Castán, José María

AU - Yu, Jing

AU - Blanchard, Philippe

AU - Sojic, Neso

AU - Ahn, Hyun S.

AU - Walker, Bright

AU - Cabanetos, Clément

AU - Bouffier, Laurent

N1 - Funding Information: A. L. D. acknowledges the University of Bordeaux for a PhD studentship. L. B. thanks the CNRS and the Department Science & Technology of the University of Bordeaux for funding (AAP 2017, project MICRO-REDOX). J. M. A. C. thanks the European Union's Horizon 2020 research and innovation program under Marie Sklodowska-Curie Grant agreement No. 722651 (SEPOMO). C. C. thanks the ANR for the funding of the “BTXI-APOGEE” project (ANR-20-CE05-0029). N. S. thanks the Eurorégion Nouvelle-Aquitaine Euskadi Navarre for funding the ECLICARE project. Funding Information: A. L. D. acknowledges the University of Bordeaux for a PhD studentship. L. B. thanks the CNRS and the Department Science & Technology of the University of Bordeaux for funding (AAP 2017, project MICRO‐REDOX). J. M. A. C. thanks the European Union's Horizon 2020 research and innovation program under Marie Sklodowska‐Curie Grant agreement No. 722651 (SEPOMO). C. C. thanks the ANR for the funding of the “BTXI‐APOGEE” project (ANR‐20‐CE05‐0029). N. S. thanks the Eurorégion Nouvelle‐Aquitaine Euskadi Navarre for funding the ECLICARE project. Publisher Copyright: © 2022 Wiley-VCH GmbH.

PY - 2022/12/27

Y1 - 2022/12/27

N2 - Overlooked for years, the promising benzothioxanthene dicarboximide (BTXI) structure is nonetheless known to be an excellent fluorophore. As a further step towards the exploration of this rylene structure, the generation of electrochemiluminescence (ECL) in acetonitrile solutions is investigated herein as well as its direct comparison with a diphenylamine (DPA) derivative. Electrochemical characterization shows that the bare BTXI can be reversibly reduced or oxidized, characteristics which suggest the possibility that the electrogenerated reactive species can be exploited in the context of ECL. As a result, the BTXI moiety was found to be ECL-active in both annihilation and co-reactant mechanisms. Tri-n-propylamine (TPA) and benzoyl peroxide (BPO) were selected as sacrificial co-reactants for promoting ECL. An ECL efficiency of 13 % (BTXI) and 6 % (BTXI-DPA) compared to that of Ru(bpy)32+ was found when using TPA in oxidative ECL. Moreover, the ECL efficiency increased to 75 % and 55 % of Ru(bpy)32+ with BPO (i. e. reductive-oxidation ECL) for BTXI and BTXI-DPA, respectively. These results can be understood by calculating the free enthalpy of the redox reactions associated with each ECL pathway. Although the BTXI-DPA red emitter exhibits more suitable thermodynamic properties, the BTXI green emitter is nonetheless more effective in combination with a co-reactant due to a much larger photoluminescence quantum yield. The ECL spectra of the two molecules are compared to their photoluminescence spectra, revealing the involvement of the same excited states in the two different photoemission processes. In turn, the chemical engineering of BTXI is shown to be an effective platform for achieving tuneable ECL generation.

AB - Overlooked for years, the promising benzothioxanthene dicarboximide (BTXI) structure is nonetheless known to be an excellent fluorophore. As a further step towards the exploration of this rylene structure, the generation of electrochemiluminescence (ECL) in acetonitrile solutions is investigated herein as well as its direct comparison with a diphenylamine (DPA) derivative. Electrochemical characterization shows that the bare BTXI can be reversibly reduced or oxidized, characteristics which suggest the possibility that the electrogenerated reactive species can be exploited in the context of ECL. As a result, the BTXI moiety was found to be ECL-active in both annihilation and co-reactant mechanisms. Tri-n-propylamine (TPA) and benzoyl peroxide (BPO) were selected as sacrificial co-reactants for promoting ECL. An ECL efficiency of 13 % (BTXI) and 6 % (BTXI-DPA) compared to that of Ru(bpy)32+ was found when using TPA in oxidative ECL. Moreover, the ECL efficiency increased to 75 % and 55 % of Ru(bpy)32+ with BPO (i. e. reductive-oxidation ECL) for BTXI and BTXI-DPA, respectively. These results can be understood by calculating the free enthalpy of the redox reactions associated with each ECL pathway. Although the BTXI-DPA red emitter exhibits more suitable thermodynamic properties, the BTXI green emitter is nonetheless more effective in combination with a co-reactant due to a much larger photoluminescence quantum yield. The ECL spectra of the two molecules are compared to their photoluminescence spectra, revealing the involvement of the same excited states in the two different photoemission processes. In turn, the chemical engineering of BTXI is shown to be an effective platform for achieving tuneable ECL generation.

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Benzothioxanthene Dicarboximide as a Tuneable Electrogenerated Chemiluminescence Dye

Abstract

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