Solution-Processable Quinoidal Dithioalkylterthiophene-Based Small Molecules Pseudo-Pentathienoacenes via an Intramolecular S···S Lock for High-Performance n-Type Organic Field-Effect Transistors

Sureshraju Vegiraju; Alfonsina Abat Amelenan Torimtubun; Po Shen Lin; Hsin Chia Tsai; Wei Chieh Lien; Cheng Shiun Chen; Guan Yu He; Chih Yu Lin; Ding Zheng; Yi Fan Huang; Yi Ching Wu; Shueh Lin Yau; Gene Hsiang Lee; Shih Huang Tung; Chien Lung Wang; Cheng Liang Liu; Ming Chou Chen; Antonio Facchetti

doi:10.1021/acsami.0c03477

Solution-Processable Quinoidal Dithioalkylterthiophene-Based Small Molecules Pseudo-Pentathienoacenes via an Intramolecular S···S Lock for High-Performance n-Type Organic Field-Effect Transistors

Sureshraju Vegiraju, Alfonsina Abat Amelenan Torimtubun, Po Shen Lin, Hsin Chia Tsai, Wei Chieh Lien, Cheng Shiun Chen, Guan Yu He, Chih Yu Lin, Ding Zheng, Yi Fan Huang, Yi Ching Wu, Shueh Lin Yau, Gene Hsiang Lee, Shih Huang Tung, Chien Lung Wang, Cheng Liang Liu^*, Ming Chou Chen^*, Antonio Facchetti

^*Corresponding author for this work

Chemistry

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

28 Scopus citations

Abstract

A new organic small-molecule family comprising tetracyanoquinodimethane-substituted quinoidal dithioalky(SR)terthiophenes (DSTQs) (DSTQ-6 (1); SR = SC₆H₁₃, DSTQ-10 (2); SR = SC₁₀H₂₁, DSTQ-14 (3); SR = SC₁₀H₂₁) was synthesized and contrasted with a nonthioalkylated analogue (DRTQ-14 (4); R = C₁₄H₂₉). The physical, electrochemical, and electrical properties of these new compounds are thoroughly investigated. Optimized geometries obtained from density functional theory calculations and single-crystal X-ray diffraction reveal the planarity of the SR-containing DSTQ core. DSTQs pack in a slipped π-πstacked two-dimensional arrangement, with a short intermolecular stacking distance of 3.55 Å and short intermolecular S···N contacts of 3.56 Å. Thin-film morphological analysis by grazing incident X-ray diffraction reveals that all DSTQ molecules are packed in an edge-on fashion on the substrate. The favorable molecular packing, the high core planarity, and very low lowest unoccupied molecular orbital (LUMO) energy level (-4.2 eV) suggest that DSTQs could be electron-transporting semiconductors. Organic field-effect transistors based on solution-sheared DSTQ-14 exhibit the highest electron mobility of 0.77 cm² V^-1 s^-1 with good ambient stability, which is the highest value reported to date for such a solution process terthiophene-based small molecular semiconductor. These results demonstrate that the device performance of solution-sheared DSTQs can be improved by side chain engineering.

Original language	English (US)
Pages (from-to)	25081-25091
Number of pages	11
Journal	ACS Applied Materials and Interfaces
Volume	12
Issue number	22
DOIs	https://doi.org/10.1021/acsami.0c03477
State	Published - Jun 3 2020

Funding

The authors acknowledge the financial support received from the Ministry of Science and Technology of Taiwan (MOST). C.-L.L. acknowledges the financial support from the Young Scholar Fellowship Program (Columbus Program) by MOST in Taiwan, under Grant (MOST 109-2636-E-008-005). The authors also thank Beamline B13A1/B17A1 (National Synchrotron Radiation Research Center (NSRRC) of Taiwan for providing beam time.

Keywords

dithioalkylterthiophene
organic field-effect transistors
pseudo-pentathienoacenes
quinoidal
tetracyanoquinodimethane

ASJC Scopus subject areas

General Materials Science

Access to Document

10.1021/acsami.0c03477

Cite this

Vegiraju, S., Amelenan Torimtubun, A. A., Lin, P. S., Tsai, H. C., Lien, W. C., Chen, C. S., He, G. Y., Lin, C. Y., Zheng, D., Huang, Y. F., Wu, Y. C., Yau, S. L., Lee, G. H., Tung, S. H., Wang, C. L., Liu, C. L., Chen, M. C., & Facchetti, A. (2020). Solution-Processable Quinoidal Dithioalkylterthiophene-Based Small Molecules Pseudo-Pentathienoacenes via an Intramolecular S···S Lock for High-Performance n-Type Organic Field-Effect Transistors. ACS Applied Materials and Interfaces, 12(22), 25081-25091. https://doi.org/10.1021/acsami.0c03477

@article{c45cf3f674e04efeb53649d3cdd30a2b,

title = "Solution-Processable Quinoidal Dithioalkylterthiophene-Based Small Molecules Pseudo-Pentathienoacenes via an Intramolecular S···S Lock for High-Performance n-Type Organic Field-Effect Transistors",

abstract = "A new organic small-molecule family comprising tetracyanoquinodimethane-substituted quinoidal dithioalky(SR)terthiophenes (DSTQs) (DSTQ-6 (1); SR = SC6H13, DSTQ-10 (2); SR = SC10H21, DSTQ-14 (3); SR = SC10H21) was synthesized and contrasted with a nonthioalkylated analogue (DRTQ-14 (4); R = C14H29). The physical, electrochemical, and electrical properties of these new compounds are thoroughly investigated. Optimized geometries obtained from density functional theory calculations and single-crystal X-ray diffraction reveal the planarity of the SR-containing DSTQ core. DSTQs pack in a slipped π-πstacked two-dimensional arrangement, with a short intermolecular stacking distance of 3.55 {\AA} and short intermolecular S···N contacts of 3.56 {\AA}. Thin-film morphological analysis by grazing incident X-ray diffraction reveals that all DSTQ molecules are packed in an edge-on fashion on the substrate. The favorable molecular packing, the high core planarity, and very low lowest unoccupied molecular orbital (LUMO) energy level (-4.2 eV) suggest that DSTQs could be electron-transporting semiconductors. Organic field-effect transistors based on solution-sheared DSTQ-14 exhibit the highest electron mobility of 0.77 cm2 V-1 s-1 with good ambient stability, which is the highest value reported to date for such a solution process terthiophene-based small molecular semiconductor. These results demonstrate that the device performance of solution-sheared DSTQs can be improved by side chain engineering.",

keywords = "dithioalkylterthiophene, organic field-effect transistors, pseudo-pentathienoacenes, quinoidal, tetracyanoquinodimethane",

author = "Sureshraju Vegiraju and {Amelenan Torimtubun}, {Alfonsina Abat} and Lin, {Po Shen} and Tsai, {Hsin Chia} and Lien, {Wei Chieh} and Chen, {Cheng Shiun} and He, {Guan Yu} and Lin, {Chih Yu} and Ding Zheng and Huang, {Yi Fan} and Wu, {Yi Ching} and Yau, {Shueh Lin} and Lee, {Gene Hsiang} and Tung, {Shih Huang} and Wang, {Chien Lung} and Liu, {Cheng Liang} and Chen, {Ming Chou} and Antonio Facchetti",

note = "Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society.",

year = "2020",

month = jun,

day = "3",

doi = "10.1021/acsami.0c03477",

language = "English (US)",

volume = "12",

pages = "25081--25091",

journal = "ACS Applied Materials and Interfaces",

issn = "1944-8244",

publisher = "American Chemical Society",

number = "22",

}

Vegiraju, S, Amelenan Torimtubun, AA, Lin, PS, Tsai, HC, Lien, WC, Chen, CS, He, GY, Lin, CY, Zheng, D, Huang, YF, Wu, YC, Yau, SL, Lee, GH, Tung, SH, Wang, CL, Liu, CL, Chen, MC & Facchetti, A 2020, 'Solution-Processable Quinoidal Dithioalkylterthiophene-Based Small Molecules Pseudo-Pentathienoacenes via an Intramolecular S···S Lock for High-Performance n-Type Organic Field-Effect Transistors', ACS Applied Materials and Interfaces, vol. 12, no. 22, pp. 25081-25091. https://doi.org/10.1021/acsami.0c03477

Solution-Processable Quinoidal Dithioalkylterthiophene-Based Small Molecules Pseudo-Pentathienoacenes via an Intramolecular S···S Lock for High-Performance n-Type Organic Field-Effect Transistors. / Vegiraju, Sureshraju; Amelenan Torimtubun, Alfonsina Abat; Lin, Po Shen et al.
In: ACS Applied Materials and Interfaces, Vol. 12, No. 22, 03.06.2020, p. 25081-25091.

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

TY - JOUR

T1 - Solution-Processable Quinoidal Dithioalkylterthiophene-Based Small Molecules Pseudo-Pentathienoacenes via an Intramolecular S···S Lock for High-Performance n-Type Organic Field-Effect Transistors

AU - Vegiraju, Sureshraju

AU - Amelenan Torimtubun, Alfonsina Abat

AU - Lin, Po Shen

AU - Tsai, Hsin Chia

AU - Lien, Wei Chieh

AU - Chen, Cheng Shiun

AU - He, Guan Yu

AU - Lin, Chih Yu

AU - Zheng, Ding

AU - Huang, Yi Fan

AU - Wu, Yi Ching

AU - Yau, Shueh Lin

AU - Lee, Gene Hsiang

AU - Tung, Shih Huang

AU - Wang, Chien Lung

AU - Liu, Cheng Liang

AU - Chen, Ming Chou

AU - Facchetti, Antonio

PY - 2020/6/3

Y1 - 2020/6/3

N2 - A new organic small-molecule family comprising tetracyanoquinodimethane-substituted quinoidal dithioalky(SR)terthiophenes (DSTQs) (DSTQ-6 (1); SR = SC6H13, DSTQ-10 (2); SR = SC10H21, DSTQ-14 (3); SR = SC10H21) was synthesized and contrasted with a nonthioalkylated analogue (DRTQ-14 (4); R = C14H29). The physical, electrochemical, and electrical properties of these new compounds are thoroughly investigated. Optimized geometries obtained from density functional theory calculations and single-crystal X-ray diffraction reveal the planarity of the SR-containing DSTQ core. DSTQs pack in a slipped π-πstacked two-dimensional arrangement, with a short intermolecular stacking distance of 3.55 Å and short intermolecular S···N contacts of 3.56 Å. Thin-film morphological analysis by grazing incident X-ray diffraction reveals that all DSTQ molecules are packed in an edge-on fashion on the substrate. The favorable molecular packing, the high core planarity, and very low lowest unoccupied molecular orbital (LUMO) energy level (-4.2 eV) suggest that DSTQs could be electron-transporting semiconductors. Organic field-effect transistors based on solution-sheared DSTQ-14 exhibit the highest electron mobility of 0.77 cm2 V-1 s-1 with good ambient stability, which is the highest value reported to date for such a solution process terthiophene-based small molecular semiconductor. These results demonstrate that the device performance of solution-sheared DSTQs can be improved by side chain engineering.

AB - A new organic small-molecule family comprising tetracyanoquinodimethane-substituted quinoidal dithioalky(SR)terthiophenes (DSTQs) (DSTQ-6 (1); SR = SC6H13, DSTQ-10 (2); SR = SC10H21, DSTQ-14 (3); SR = SC10H21) was synthesized and contrasted with a nonthioalkylated analogue (DRTQ-14 (4); R = C14H29). The physical, electrochemical, and electrical properties of these new compounds are thoroughly investigated. Optimized geometries obtained from density functional theory calculations and single-crystal X-ray diffraction reveal the planarity of the SR-containing DSTQ core. DSTQs pack in a slipped π-πstacked two-dimensional arrangement, with a short intermolecular stacking distance of 3.55 Å and short intermolecular S···N contacts of 3.56 Å. Thin-film morphological analysis by grazing incident X-ray diffraction reveals that all DSTQ molecules are packed in an edge-on fashion on the substrate. The favorable molecular packing, the high core planarity, and very low lowest unoccupied molecular orbital (LUMO) energy level (-4.2 eV) suggest that DSTQs could be electron-transporting semiconductors. Organic field-effect transistors based on solution-sheared DSTQ-14 exhibit the highest electron mobility of 0.77 cm2 V-1 s-1 with good ambient stability, which is the highest value reported to date for such a solution process terthiophene-based small molecular semiconductor. These results demonstrate that the device performance of solution-sheared DSTQs can be improved by side chain engineering.

KW - dithioalkylterthiophene

KW - organic field-effect transistors

KW - pseudo-pentathienoacenes

KW - quinoidal

KW - tetracyanoquinodimethane

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EP - 25091

JO - ACS Applied Materials and Interfaces

JF - ACS Applied Materials and Interfaces

IS - 22

ER -

Vegiraju S, Amelenan Torimtubun AA, Lin PS, Tsai HC, Lien WC, Chen CS et al. Solution-Processable Quinoidal Dithioalkylterthiophene-Based Small Molecules Pseudo-Pentathienoacenes via an Intramolecular S···S Lock for High-Performance n-Type Organic Field-Effect Transistors. ACS Applied Materials and Interfaces. 2020 Jun 3;12(22):25081-25091. doi: 10.1021/acsami.0c03477

Solution-Processable Quinoidal Dithioalkylterthiophene-Based Small Molecules Pseudo-Pentathienoacenes via an Intramolecular S···S Lock for High-Performance n-Type Organic Field-Effect Transistors

Abstract

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CCDC 1916104: Experimental Crystal Structure Determination

CCDC 1916105: Experimental Crystal Structure Determination

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Solution-Processable Quinoidal Dithioalkylterthiophene-Based Small Molecules Pseudo-Pentathienoacenes via an Intramolecular S···S Lock for High-Performance n-Type Organic Field-Effect Transistors

Abstract

Funding

Keywords

ASJC Scopus subject areas

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Datasets

CCDC 1916104: Experimental Crystal Structure Determination

CCDC 1916105: Experimental Crystal Structure Determination

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