Naphthalene Bis(4,8-diamino-1,5-dicarboxyl)amide Building Block for Semiconducting Polymers

Brian J. Eckstein; Ferdinand S. Melkonyan; Eric F. Manley; Simone Fabiano; Aidan R. Mouat; Lin X. Chen; Antonio Facchetti; Tobin J. Marks

doi:10.1021/jacs.7b07750

Naphthalene Bis(4,8-diamino-1,5-dicarboxyl)amide Building Block for Semiconducting Polymers

Brian J. Eckstein, Ferdinand S. Melkonyan^*, Eric F. Manley, Simone Fabiano, Aidan R. Mouat, Lin X. Chen, Antonio Facchetti, Tobin J. Marks

^*Corresponding author for this work

Chemistry

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

36 Scopus citations

Abstract

We report a new naphthalene bis(4,8-diamino-1,5-dicarboxyl)amide (NBA) building block for polymeric semiconductors. Computational modeling suggests that regio-connectivity at the 2,6- or 3,7-NBA positions strongly modulates polymer backbone torsion and, therefore, intramolecular π-conjugation and aggregation. Optical, electrochemical, and X-ray diffraction characterization of 3,7- and 2,6-dithienyl-substituted NBA molecules and corresponding isomeric NBA-bithiophene copolymers P1 and P2, respectively, reveals the key role of regio-connectivity. Charge transport measurements demonstrate that while the twisted 3,7-NDA-based P1 is a poor semiconductor, the planar 2,6-functionalized NBA polymers (P2-P4) exhibit ambipolarity, with μ_e and μ_h of up to 0.39 and 0.32 cm²/(V·s), respectively.

Original language	English (US)
Pages (from-to)	14356-14359
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	139
Issue number	41
DOIs	https://doi.org/10.1021/jacs.7b07750
State	Published - Oct 18 2017

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.7b07750

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@article{463eb87f48c74aa59e57f6fbfb4ab0bd,

title = "Naphthalene Bis(4,8-diamino-1,5-dicarboxyl)amide Building Block for Semiconducting Polymers",

abstract = "We report a new naphthalene bis(4,8-diamino-1,5-dicarboxyl)amide (NBA) building block for polymeric semiconductors. Computational modeling suggests that regio-connectivity at the 2,6- or 3,7-NBA positions strongly modulates polymer backbone torsion and, therefore, intramolecular π-conjugation and aggregation. Optical, electrochemical, and X-ray diffraction characterization of 3,7- and 2,6-dithienyl-substituted NBA molecules and corresponding isomeric NBA-bithiophene copolymers P1 and P2, respectively, reveals the key role of regio-connectivity. Charge transport measurements demonstrate that while the twisted 3,7-NDA-based P1 is a poor semiconductor, the planar 2,6-functionalized NBA polymers (P2-P4) exhibit ambipolarity, with μe and μh of up to 0.39 and 0.32 cm2/(V·s), respectively.",

author = "Eckstein, {Brian J.} and Melkonyan, {Ferdinand S.} and Manley, {Eric F.} and Simone Fabiano and Mouat, {Aidan R.} and Chen, {Lin X.} and Antonio Facchetti and Marks, {Tobin J.}",

note = "Funding Information: This research was supported in part by Argonne-Northwestern Solar Energy Research (ANSER) Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award Number DE-SC0001059 (B.J.E., polymer synthesis), and by AFOSR grant FA9550-15-1-0044 (A.F., synthetic design). F.S.M. was supported by award 70NANB14H012 from U.S. Department of Commerce, and E.F.M. by Qatar NPRP grant 7-286-1-046. This work was performed with financial assistance under award 70NANB14H012 from the U.S. Department of Commerce, National Institute of Standards and Technology, as part of the Center for Hierarchical Materials Design (CHiMaD). A.F. thanks the Shenzhen Peacock Plan project (KQTD20140630110339343) for financial support. S.F. thanks VINNOVA (2015-04859) and the Swedish Research Council (2016-03979) for financial support. Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

month = oct,

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doi = "10.1021/jacs.7b07750",

language = "English (US)",

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T1 - Naphthalene Bis(4,8-diamino-1,5-dicarboxyl)amide Building Block for Semiconducting Polymers

AU - Eckstein, Brian J.

AU - Melkonyan, Ferdinand S.

AU - Manley, Eric F.

AU - Fabiano, Simone

AU - Mouat, Aidan R.

AU - Chen, Lin X.

AU - Facchetti, Antonio

AU - Marks, Tobin J.

N1 - Funding Information: This research was supported in part by Argonne-Northwestern Solar Energy Research (ANSER) Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award Number DE-SC0001059 (B.J.E., polymer synthesis), and by AFOSR grant FA9550-15-1-0044 (A.F., synthetic design). F.S.M. was supported by award 70NANB14H012 from U.S. Department of Commerce, and E.F.M. by Qatar NPRP grant 7-286-1-046. This work was performed with financial assistance under award 70NANB14H012 from the U.S. Department of Commerce, National Institute of Standards and Technology, as part of the Center for Hierarchical Materials Design (CHiMaD). A.F. thanks the Shenzhen Peacock Plan project (KQTD20140630110339343) for financial support. S.F. thanks VINNOVA (2015-04859) and the Swedish Research Council (2016-03979) for financial support. Publisher Copyright: © 2017 American Chemical Society.

PY - 2017/10/18

Y1 - 2017/10/18

N2 - We report a new naphthalene bis(4,8-diamino-1,5-dicarboxyl)amide (NBA) building block for polymeric semiconductors. Computational modeling suggests that regio-connectivity at the 2,6- or 3,7-NBA positions strongly modulates polymer backbone torsion and, therefore, intramolecular π-conjugation and aggregation. Optical, electrochemical, and X-ray diffraction characterization of 3,7- and 2,6-dithienyl-substituted NBA molecules and corresponding isomeric NBA-bithiophene copolymers P1 and P2, respectively, reveals the key role of regio-connectivity. Charge transport measurements demonstrate that while the twisted 3,7-NDA-based P1 is a poor semiconductor, the planar 2,6-functionalized NBA polymers (P2-P4) exhibit ambipolarity, with μe and μh of up to 0.39 and 0.32 cm2/(V·s), respectively.

AB - We report a new naphthalene bis(4,8-diamino-1,5-dicarboxyl)amide (NBA) building block for polymeric semiconductors. Computational modeling suggests that regio-connectivity at the 2,6- or 3,7-NBA positions strongly modulates polymer backbone torsion and, therefore, intramolecular π-conjugation and aggregation. Optical, electrochemical, and X-ray diffraction characterization of 3,7- and 2,6-dithienyl-substituted NBA molecules and corresponding isomeric NBA-bithiophene copolymers P1 and P2, respectively, reveals the key role of regio-connectivity. Charge transport measurements demonstrate that while the twisted 3,7-NDA-based P1 is a poor semiconductor, the planar 2,6-functionalized NBA polymers (P2-P4) exhibit ambipolarity, with μe and μh of up to 0.39 and 0.32 cm2/(V·s), respectively.

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 41

ER -

Naphthalene Bis(4,8-diamino-1,5-dicarboxyl)amide Building Block for Semiconducting Polymers

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CCDC 1576724: Experimental Crystal Structure Determination

CCDC 1576725: Experimental Crystal Structure Determination

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Naphthalene Bis(4,8-diamino-1,5-dicarboxyl)amide Building Block for Semiconducting Polymers

Abstract

ASJC Scopus subject areas

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CCDC 1576724: Experimental Crystal Structure Determination

CCDC 1576725: Experimental Crystal Structure Determination

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