Tuning the antiaromatic character and charge transport of pentalene-based antiaromatic compounds by substitution

Jianglin Wu; Yao Chen; Jueshan Liu; Zhenguo Pang; Guoping Li; Zhiyun Lu; Yan Huang; Antonio Facchetti; Tobin J. Marks

doi:10.1039/d1tc03156b

Tuning the antiaromatic character and charge transport of pentalene-based antiaromatic compounds by substitution

Jianglin Wu, Yao Chen, Jueshan Liu, Zhenguo Pang, Guoping Li, Zhiyun Lu, Yan Huang^*, Antonio Facchetti^*, Tobin J. Marks^*

^*Corresponding author for this work

Chemistry

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

13 Scopus citations

Abstract

Understanding the structure-property relationships in antiaromatic molecules is crucial for controlling their electronic properties and designing new organic optoelectronic materials. Here we report the design, synthesis, and characterization of three new antiaromatic molecules (Pn, n = 1-4) based on the pentalene (P) antiaromatic core, to investigate how electron-donating and electron-accepting substituents affect P1-P4 properties. As expected, the optical, HOMO and LUMO energy levels and electronic structure are greatly modulated by core substitution. Compared to the unsubstituted compound (P1), P3 and P4 containing strong electron-withdrawing units reduced antiaromaticity as assessed by nucleus-independent chemical shift (NICS) calculations compared with P2, which is functionalized with strong electron-donating units, showing that substitution strongly tunes local antiaromaticity. Organic field-effect transistors (OFETs) fabricated using these materials indicate that P2 has an average hole mobility of ∼10-4 cm2 V-1 s-1 while P3 has an average electron mobility of up to 0.03 cm2 V-1 s-1, versus FET-inactive P1. Therefore, introduction of strong π-extended electron-withdrawing or electron-donating substituents onto an antiaromatic core is an effective strategy to switch-on charge transport capacity.

Original language	English (US)
Pages (from-to)	2724-2731
Number of pages	8
Journal	Journal of Materials Chemistry C
Volume	10
Issue number	7
DOIs	https://doi.org/10.1039/d1tc03156b
State	Published - Feb 21 2022

Funding

We acknowledge the financial support for this work from the National Natural Science Foundation of China (project no. 21875148) (Y. H., Z. L., J. W., J. L.). T. M., A. F., and Y. C., J. W. are grateful to the Center for Light Energy Activated Redox Processes (LEAP), an Energy Frontier Research Center funded by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences under award DE-SC0001059 (J. W.: fabricating device and other characterization, Y. C. and G. Li: materials synthesis, A. F. and T. J. M.: project advising), AFOSR grant FA9550-18-1-0320, the Flexterra Corporation, and the Office of Naval Research Contract N00014-20-1-2116. The use of the Advanced Photon Source, an Office of Science User Facility operated by the US DOE Office of Science by Argonne National Laboratory, was supported by the US DOE under contract DE-AC02-06CH11357. J. W. acknowledges the joint-PhD program supported by the China Scholarship Council (No. 201906240142) for a fellowship.

ASJC Scopus subject areas

General Chemistry
Materials Chemistry

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10.1039/d1tc03156b

Cite this

@article{59c90c56e6f94b0080f9fe74bc50b991,

title = "Tuning the antiaromatic character and charge transport of pentalene-based antiaromatic compounds by substitution",

abstract = "Understanding the structure-property relationships in antiaromatic molecules is crucial for controlling their electronic properties and designing new organic optoelectronic materials. Here we report the design, synthesis, and characterization of three new antiaromatic molecules (Pn, n = 1-4) based on the pentalene (P) antiaromatic core, to investigate how electron-donating and electron-accepting substituents affect P1-P4 properties. As expected, the optical, HOMO and LUMO energy levels and electronic structure are greatly modulated by core substitution. Compared to the unsubstituted compound (P1), P3 and P4 containing strong electron-withdrawing units reduced antiaromaticity as assessed by nucleus-independent chemical shift (NICS) calculations compared with P2, which is functionalized with strong electron-donating units, showing that substitution strongly tunes local antiaromaticity. Organic field-effect transistors (OFETs) fabricated using these materials indicate that P2 has an average hole mobility of ∼10-4 cm2 V-1 s-1 while P3 has an average electron mobility of up to 0.03 cm2 V-1 s-1, versus FET-inactive P1. Therefore, introduction of strong π-extended electron-withdrawing or electron-donating substituents onto an antiaromatic core is an effective strategy to switch-on charge transport capacity.",

author = "Jianglin Wu and Yao Chen and Jueshan Liu and Zhenguo Pang and Guoping Li and Zhiyun Lu and Yan Huang and Antonio Facchetti and Marks, {Tobin J.}",

note = "Funding Information: We acknowledge the financial support for this work from the National Natural Science Foundation of China (project no. 21875148) (Y. H., Z. L., J. W., J. L.). T. M., A. F., and Y. C., J. W. are grateful to the Center for Light Energy Activated Redox Processes (LEAP), an Energy Frontier Research Center funded by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences under award DE-SC0001059 (J. W.: fabricating device and other characterization, Y. C. and G. Li: materials synthesis, A. F. and T. J. M.: project advising), AFOSR grant FA9550-18-1-0320, the Flexterra Corporation, and the Office of Naval Research Contract N00014-20-1-2116. The use of the Advanced Photon Source, an Office of Science User Facility operated by the US DOE Office of Science by Argonne National Laboratory, was supported by the US DOE under contract DE-AC02-06CH11357. J. W. acknowledges the joint-PhD program supported by the China Scholarship Council (No. 201906240142) for a fellowship. Publisher Copyright: {\textcopyright} The Royal Society of Chemistry.",

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T1 - Tuning the antiaromatic character and charge transport of pentalene-based antiaromatic compounds by substitution

AU - Wu, Jianglin

AU - Chen, Yao

AU - Liu, Jueshan

AU - Pang, Zhenguo

AU - Li, Guoping

AU - Lu, Zhiyun

AU - Huang, Yan

AU - Facchetti, Antonio

AU - Marks, Tobin J.

N1 - Funding Information: We acknowledge the financial support for this work from the National Natural Science Foundation of China (project no. 21875148) (Y. H., Z. L., J. W., J. L.). T. M., A. F., and Y. C., J. W. are grateful to the Center for Light Energy Activated Redox Processes (LEAP), an Energy Frontier Research Center funded by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences under award DE-SC0001059 (J. W.: fabricating device and other characterization, Y. C. and G. Li: materials synthesis, A. F. and T. J. M.: project advising), AFOSR grant FA9550-18-1-0320, the Flexterra Corporation, and the Office of Naval Research Contract N00014-20-1-2116. The use of the Advanced Photon Source, an Office of Science User Facility operated by the US DOE Office of Science by Argonne National Laboratory, was supported by the US DOE under contract DE-AC02-06CH11357. J. W. acknowledges the joint-PhD program supported by the China Scholarship Council (No. 201906240142) for a fellowship. Publisher Copyright: © The Royal Society of Chemistry.

PY - 2022/2/21

Y1 - 2022/2/21

N2 - Understanding the structure-property relationships in antiaromatic molecules is crucial for controlling their electronic properties and designing new organic optoelectronic materials. Here we report the design, synthesis, and characterization of three new antiaromatic molecules (Pn, n = 1-4) based on the pentalene (P) antiaromatic core, to investigate how electron-donating and electron-accepting substituents affect P1-P4 properties. As expected, the optical, HOMO and LUMO energy levels and electronic structure are greatly modulated by core substitution. Compared to the unsubstituted compound (P1), P3 and P4 containing strong electron-withdrawing units reduced antiaromaticity as assessed by nucleus-independent chemical shift (NICS) calculations compared with P2, which is functionalized with strong electron-donating units, showing that substitution strongly tunes local antiaromaticity. Organic field-effect transistors (OFETs) fabricated using these materials indicate that P2 has an average hole mobility of ∼10-4 cm2 V-1 s-1 while P3 has an average electron mobility of up to 0.03 cm2 V-1 s-1, versus FET-inactive P1. Therefore, introduction of strong π-extended electron-withdrawing or electron-donating substituents onto an antiaromatic core is an effective strategy to switch-on charge transport capacity.

AB - Understanding the structure-property relationships in antiaromatic molecules is crucial for controlling their electronic properties and designing new organic optoelectronic materials. Here we report the design, synthesis, and characterization of three new antiaromatic molecules (Pn, n = 1-4) based on the pentalene (P) antiaromatic core, to investigate how electron-donating and electron-accepting substituents affect P1-P4 properties. As expected, the optical, HOMO and LUMO energy levels and electronic structure are greatly modulated by core substitution. Compared to the unsubstituted compound (P1), P3 and P4 containing strong electron-withdrawing units reduced antiaromaticity as assessed by nucleus-independent chemical shift (NICS) calculations compared with P2, which is functionalized with strong electron-donating units, showing that substitution strongly tunes local antiaromaticity. Organic field-effect transistors (OFETs) fabricated using these materials indicate that P2 has an average hole mobility of ∼10-4 cm2 V-1 s-1 while P3 has an average electron mobility of up to 0.03 cm2 V-1 s-1, versus FET-inactive P1. Therefore, introduction of strong π-extended electron-withdrawing or electron-donating substituents onto an antiaromatic core is an effective strategy to switch-on charge transport capacity.

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Tuning the antiaromatic character and charge transport of pentalene-based antiaromatic compounds by substitution

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CCDC 2042120: Experimental Crystal Structure Determination

CCDC 2042122: Experimental Crystal Structure Determination

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Tuning the antiaromatic character and charge transport of pentalene-based antiaromatic compounds by substitution

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CCDC 2042120: Experimental Crystal Structure Determination

CCDC 2042122: Experimental Crystal Structure Determination

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