Reactivity of an air-stable dihydrobenzoimidazole n-dopant with organic semiconductor molecules

Samik Jhulki; Hio Ieng Un; Yi Fan Ding; Chad Risko; Swagat K. Mohapatra; Jian Pei; Stephen Barlow; Seth R. Marder

doi:10.1016/j.chempr.2021.01.020

Reactivity of an air-stable dihydrobenzoimidazole n-dopant with organic semiconductor molecules

Samik Jhulki, Hio Ieng Un, Yi Fan Ding, Chad Risko, Swagat K. Mohapatra, Jian Pei, Stephen Barlow, Seth R. Marder

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

32 Scopus citations

Abstract

1,3-Dimethyl-2-(4-(dimethylamino)phenyl)-2,4-dihydro-1H-benzoimidazole, N-DMBI-H, is widely used as an air-stable n-dopant for organic semiconductors. Here, its reactivity is investigated with a variety of imide- and amide-containing semiconductor molecules that have reduction potentials in the range −0.54 to −1.10 V versus ferrocene. Reaction rates correlate poorly with these potentials. The more reactive of the imides form the corresponding radical anions cleanly, but kinetic isotope studies using N-DMBI-D indicate that the reaction proceeds via an initial hydride- or hydrogen-transfer step. For an amide- and ester-rigidified bis(styryl)benzene derivative the hydride-reduced product is stable under an inert atmosphere and can be observed directly; the radical anion can only be obtained in sub-stoichiometric yield and under certain reaction conditions. On the other hand, (N-DMBI)₂ rapidly reduces all the imides and amides examined to the corresponding radical anions. The implications of these findings for dopant selection and use are discussed.

Original language	English
Pages (from-to)	1050-1065
Number of pages	16
Journal	Chem
Volume	7
Issue number	4
DOIs	https://doi.org/10.1016/j.chempr.2021.01.020
State	Published - Apr 8 2021

Bibliographical note

Funding Information:
This work was supported by: the National Science Foundation (through DMR-1807797 and DMR-1729737); the United States-India Educational Foundation and Institute of International Education (through a Fulbright-Nehru Postdoctoral Fellowship to S.J. grant no. 2266/FNPDR/2017); the National Natural Science Foundation of China (through 21790360, 21722201, and 21420102005); the Office of Naval Research Young Investigator Program (N00014-18-1-2448); and the University of Kentucky Information Technology Department and the University of Kentucky Center for Computational Sciences (CCS) (for provision of supercomputing resources on the Lipscomb High-Performance Computing Cluster). We thank Khaled Al Kurdi for providing 3c, Ye-Xin Wang for assistance with ESR measurements, and Yadong Zhang for providing the oxidant used for Figure S13C. Conceptualization, J.P. S.B. and S.R.M.; Investigation, S.J. H.-I.U. Y.-F.D. and C.R.; Resources, S.K.M.; Writing – Original Draft, S.J. H.-I.U. and S.B.; Writing – Review and Editing, all authors; Funding Acquisition, C.R. J.P. S.R.M. and S.B.; Supervision, J.P. S.B. and S.R.M. S.K.M. S.B. and S.R.M. are inventors on a patent (U.S. patent 8,912,535) relating to the use of II2 as an n-dopant.

Publisher Copyright:
© 2021 Elsevier Inc.

Keywords

SDG7: Affordable and clean energy
benzoimidazole
dopant
hydride transfer
kinetic isotope effect
mechanism
organic semiconductor
rylene diimide

ASJC Scopus subject areas

Chemistry (all)
Biochemistry
Environmental Chemistry
Chemical Engineering (all)
Biochemistry, medical
Materials Chemistry

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10.1016/j.chempr.2021.01.020

Cite this

@article{fccb7d1cbc6442079c8845dac3cb0004,

title = "Reactivity of an air-stable dihydrobenzoimidazole n-dopant with organic semiconductor molecules",

abstract = "1,3-Dimethyl-2-(4-(dimethylamino)phenyl)-2,4-dihydro-1H-benzoimidazole, N-DMBI-H, is widely used as an air-stable n-dopant for organic semiconductors. Here, its reactivity is investigated with a variety of imide- and amide-containing semiconductor molecules that have reduction potentials in the range −0.54 to −1.10 V versus ferrocene. Reaction rates correlate poorly with these potentials. The more reactive of the imides form the corresponding radical anions cleanly, but kinetic isotope studies using N-DMBI-D indicate that the reaction proceeds via an initial hydride- or hydrogen-transfer step. For an amide- and ester-rigidified bis(styryl)benzene derivative the hydride-reduced product is stable under an inert atmosphere and can be observed directly; the radical anion can only be obtained in sub-stoichiometric yield and under certain reaction conditions. On the other hand, (N-DMBI)2 rapidly reduces all the imides and amides examined to the corresponding radical anions. The implications of these findings for dopant selection and use are discussed.",

keywords = "SDG7: Affordable and clean energy, benzoimidazole, dopant, hydride transfer, kinetic isotope effect, mechanism, organic semiconductor, rylene diimide",

author = "Samik Jhulki and Un, {Hio Ieng} and Ding, {Yi Fan} and Chad Risko and Mohapatra, {Swagat K.} and Jian Pei and Stephen Barlow and Marder, {Seth R.}",

note = "Funding Information: This work was supported by: the National Science Foundation (through DMR-1807797 and DMR-1729737); the United States-India Educational Foundation and Institute of International Education (through a Fulbright-Nehru Postdoctoral Fellowship to S.J. grant no. 2266/FNPDR/2017); the National Natural Science Foundation of China (through 21790360, 21722201, and 21420102005); the Office of Naval Research Young Investigator Program (N00014-18-1-2448); and the University of Kentucky Information Technology Department and the University of Kentucky Center for Computational Sciences (CCS) (for provision of supercomputing resources on the Lipscomb High-Performance Computing Cluster). We thank Khaled Al Kurdi for providing 3c, Ye-Xin Wang for assistance with ESR measurements, and Yadong Zhang for providing the oxidant used for Figure S13C. Conceptualization, J.P. S.B. and S.R.M.; Investigation, S.J. H.-I.U. Y.-F.D. and C.R.; Resources, S.K.M.; Writing – Original Draft, S.J. H.-I.U. and S.B.; Writing – Review and Editing, all authors; Funding Acquisition, C.R. J.P. S.R.M. and S.B.; Supervision, J.P. S.B. and S.R.M. S.K.M. S.B. and S.R.M. are inventors on a patent (U.S. patent 8,912,535) relating to the use of II2 as an n-dopant. Publisher Copyright: {\textcopyright} 2021 Elsevier Inc.",

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doi = "10.1016/j.chempr.2021.01.020",

language = "English",

volume = "7",

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AU - Jhulki, Samik

AU - Un, Hio Ieng

AU - Ding, Yi Fan

AU - Risko, Chad

AU - Mohapatra, Swagat K.

AU - Pei, Jian

AU - Barlow, Stephen

AU - Marder, Seth R.

N1 - Funding Information: This work was supported by: the National Science Foundation (through DMR-1807797 and DMR-1729737); the United States-India Educational Foundation and Institute of International Education (through a Fulbright-Nehru Postdoctoral Fellowship to S.J. grant no. 2266/FNPDR/2017); the National Natural Science Foundation of China (through 21790360, 21722201, and 21420102005); the Office of Naval Research Young Investigator Program (N00014-18-1-2448); and the University of Kentucky Information Technology Department and the University of Kentucky Center for Computational Sciences (CCS) (for provision of supercomputing resources on the Lipscomb High-Performance Computing Cluster). We thank Khaled Al Kurdi for providing 3c, Ye-Xin Wang for assistance with ESR measurements, and Yadong Zhang for providing the oxidant used for Figure S13C. Conceptualization, J.P. S.B. and S.R.M.; Investigation, S.J. H.-I.U. Y.-F.D. and C.R.; Resources, S.K.M.; Writing – Original Draft, S.J. H.-I.U. and S.B.; Writing – Review and Editing, all authors; Funding Acquisition, C.R. J.P. S.R.M. and S.B.; Supervision, J.P. S.B. and S.R.M. S.K.M. S.B. and S.R.M. are inventors on a patent (U.S. patent 8,912,535) relating to the use of II2 as an n-dopant. Publisher Copyright: © 2021 Elsevier Inc.

PY - 2021/4/8

Y1 - 2021/4/8

N2 - 1,3-Dimethyl-2-(4-(dimethylamino)phenyl)-2,4-dihydro-1H-benzoimidazole, N-DMBI-H, is widely used as an air-stable n-dopant for organic semiconductors. Here, its reactivity is investigated with a variety of imide- and amide-containing semiconductor molecules that have reduction potentials in the range −0.54 to −1.10 V versus ferrocene. Reaction rates correlate poorly with these potentials. The more reactive of the imides form the corresponding radical anions cleanly, but kinetic isotope studies using N-DMBI-D indicate that the reaction proceeds via an initial hydride- or hydrogen-transfer step. For an amide- and ester-rigidified bis(styryl)benzene derivative the hydride-reduced product is stable under an inert atmosphere and can be observed directly; the radical anion can only be obtained in sub-stoichiometric yield and under certain reaction conditions. On the other hand, (N-DMBI)2 rapidly reduces all the imides and amides examined to the corresponding radical anions. The implications of these findings for dopant selection and use are discussed.

AB - 1,3-Dimethyl-2-(4-(dimethylamino)phenyl)-2,4-dihydro-1H-benzoimidazole, N-DMBI-H, is widely used as an air-stable n-dopant for organic semiconductors. Here, its reactivity is investigated with a variety of imide- and amide-containing semiconductor molecules that have reduction potentials in the range −0.54 to −1.10 V versus ferrocene. Reaction rates correlate poorly with these potentials. The more reactive of the imides form the corresponding radical anions cleanly, but kinetic isotope studies using N-DMBI-D indicate that the reaction proceeds via an initial hydride- or hydrogen-transfer step. For an amide- and ester-rigidified bis(styryl)benzene derivative the hydride-reduced product is stable under an inert atmosphere and can be observed directly; the radical anion can only be obtained in sub-stoichiometric yield and under certain reaction conditions. On the other hand, (N-DMBI)2 rapidly reduces all the imides and amides examined to the corresponding radical anions. The implications of these findings for dopant selection and use are discussed.

KW - SDG7: Affordable and clean energy

KW - benzoimidazole

KW - dopant

KW - hydride transfer

KW - kinetic isotope effect

KW - mechanism

KW - organic semiconductor

KW - rylene diimide

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ER -

Reactivity of an air-stable dihydrobenzoimidazole n-dopant with organic semiconductor molecules

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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