Semiconducting Copolymers with Naphthalene Imide/Amide π-Conjugated Units: Synthesis, Crystallography, and Systematic Structure-Property-Mobility Correlations

Yao Chen; Jianglin Wu; Shirong Lu; Antonio Facchetti; Tobin J. Marks

doi:10.1002/anie.202208201

Semiconducting Copolymers with Naphthalene Imide/Amide π-Conjugated Units: Synthesis, Crystallography, and Systematic Structure-Property-Mobility Correlations

Yao Chen, Jianglin Wu, Shirong Lu^*, Antonio Facchetti^*, Tobin J. Marks^*

^*Corresponding author for this work

Chemistry

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

11 Scopus citations

Abstract

In a series of n-type semiconducting naphthalene tetracarboxydiimide (NDI)-dithiophene (T2) copolymers, structural and electronic properties trends are systematically evaluated as the number of NDI carbonyl groups is reduced from 4 in NDI to 3 in NBL (1-amino-4,5-8-naphthalene-tricarboxylic acid-1,8-lactam-4,5-imide) to 2 in NBA (naphthalene-bis(4,8-diamino-1,5-dicarboxyl)-amide). As the NDI-T2 backbone torsional angle falls the LUMO energy rises. However, the thienyl attachment regiochemistry also plays an important role in less symmetric NBL and NBA. Electron mobility is greatest for N2200 (0.17 cm² V⁻¹ s⁻¹) followed by PNBL-3,8-T2 and PNBA-2,6-T2 (0.11 cm² V⁻¹ s⁻¹), 0.02 cm² V⁻¹ s⁻¹ in PNBL-4,8-T2, and negligible in PNBA-3,7-T2. Charge transport reflects a delicate balance between electronic backbone communication (optimum for N2200 and PNBL-4,8-T2), backbone planarity (optimum for PNBA-2,6-T2 and PNBL-3,8-T2), LUMO energy (optimum for N2200), π–π stacking distance (optimum for PNBA-2,6-T2), and film crystallinity (optimum for PNBA-2,6-T2 and N2200). These results offer generalizable insight into semiconducting copolymer design.

Original language	English (US)
Article number	e202208201
Journal	Angewandte Chemie - International Edition
Volume	61
Issue number	39
DOIs	https://doi.org/10.1002/anie.202208201
State	Published - Sep 26 2022

Funding

The authors acknowledge support from the Northwestern University MRSEC (NSF grant DMR-1720139), AFOSR (grant FA9550-18-1-0320), award 70NANB14H012 from U.S. Department of Commerce, National Institute of Standards and Technology as part of the Center for Hierarchical Materials Design, and Flexterra Inc. This work made use of the Keck-II facility, and SPID facility, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205). This work was supported by the Department of Energy under contract no. DE-AC02-05CH11231 and used resources at beamline 8-ID-E of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This work was financially supported by research grants from the Science Fund for Distinguished Young Scholars of Chongqing (cstc2020jcyj-jqX0018) and National Natural Science Foundation of China (62074149). The authors acknowledge support from the Northwestern University MRSEC (NSF grant DMR‐1720139), AFOSR (grant FA9550‐18‐1‐0320), award 70NANB14H012 from U.S. Department of Commerce, National Institute of Standards and Technology as part of the Center for Hierarchical Materials Design, and Flexterra Inc. This work made use of the Keck‐II facility, and SPID facility, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS‐1542205). This work was supported by the Department of Energy under contract no. DE‐AC02‐05CH11231 and used resources at beamline 8‐ID‐E of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE‐AC02‐06CH11357. This work was financially supported by research grants from the Science Fund for Distinguished Young Scholars of Chongqing (cstc2020jcyj‐jqX0018) and National Natural Science Foundation of China (62074149).

Keywords

Charge Transport
Crystallinity
Naphthalene Imide/Amide
Organic Electronics
Organic Semiconductors

ASJC Scopus subject areas

General Chemistry
Catalysis

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10.1002/anie.202208201

Cite this

@article{9017eb198ef849c6aedfd5ab469ad91e,

title = "Semiconducting Copolymers with Naphthalene Imide/Amide π-Conjugated Units: Synthesis, Crystallography, and Systematic Structure-Property-Mobility Correlations",

abstract = "In a series of n-type semiconducting naphthalene tetracarboxydiimide (NDI)-dithiophene (T2) copolymers, structural and electronic properties trends are systematically evaluated as the number of NDI carbonyl groups is reduced from 4 in NDI to 3 in NBL (1-amino-4,5-8-naphthalene-tricarboxylic acid-1,8-lactam-4,5-imide) to 2 in NBA (naphthalene-bis(4,8-diamino-1,5-dicarboxyl)-amide). As the NDI-T2 backbone torsional angle falls the LUMO energy rises. However, the thienyl attachment regiochemistry also plays an important role in less symmetric NBL and NBA. Electron mobility is greatest for N2200 (0.17 cm2 V−1 s−1) followed by PNBL-3,8-T2 and PNBA-2,6-T2 (0.11 cm2 V−1 s−1), 0.02 cm2 V−1 s−1 in PNBL-4,8-T2, and negligible in PNBA-3,7-T2. Charge transport reflects a delicate balance between electronic backbone communication (optimum for N2200 and PNBL-4,8-T2), backbone planarity (optimum for PNBA-2,6-T2 and PNBL-3,8-T2), LUMO energy (optimum for N2200), π–π stacking distance (optimum for PNBA-2,6-T2), and film crystallinity (optimum for PNBA-2,6-T2 and N2200). These results offer generalizable insight into semiconducting copolymer design.",

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T2 - Synthesis, Crystallography, and Systematic Structure-Property-Mobility Correlations

AU - Chen, Yao

AU - Wu, Jianglin

AU - Lu, Shirong

AU - Facchetti, Antonio

AU - Marks, Tobin J.

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AB - In a series of n-type semiconducting naphthalene tetracarboxydiimide (NDI)-dithiophene (T2) copolymers, structural and electronic properties trends are systematically evaluated as the number of NDI carbonyl groups is reduced from 4 in NDI to 3 in NBL (1-amino-4,5-8-naphthalene-tricarboxylic acid-1,8-lactam-4,5-imide) to 2 in NBA (naphthalene-bis(4,8-diamino-1,5-dicarboxyl)-amide). As the NDI-T2 backbone torsional angle falls the LUMO energy rises. However, the thienyl attachment regiochemistry also plays an important role in less symmetric NBL and NBA. Electron mobility is greatest for N2200 (0.17 cm2 V−1 s−1) followed by PNBL-3,8-T2 and PNBA-2,6-T2 (0.11 cm2 V−1 s−1), 0.02 cm2 V−1 s−1 in PNBL-4,8-T2, and negligible in PNBA-3,7-T2. Charge transport reflects a delicate balance between electronic backbone communication (optimum for N2200 and PNBL-4,8-T2), backbone planarity (optimum for PNBA-2,6-T2 and PNBL-3,8-T2), LUMO energy (optimum for N2200), π–π stacking distance (optimum for PNBA-2,6-T2), and film crystallinity (optimum for PNBA-2,6-T2 and N2200). These results offer generalizable insight into semiconducting copolymer design.

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KW - Crystallinity

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KW - Organic Semiconductors

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Semiconducting Copolymers with Naphthalene Imide/Amide π-Conjugated Units: Synthesis, Crystallography, and Systematic Structure-Property-Mobility Correlations

Abstract

Funding

Keywords

ASJC Scopus subject areas

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CCDC 2172558: Experimental Crystal Structure Determination

CCDC 2172559: Experimental Crystal Structure Determination

CCDC 2172557: Experimental Crystal Structure Determination

Cite this

Semiconducting Copolymers with Naphthalene Imide/Amide π-Conjugated Units: Synthesis, Crystallography, and Systematic Structure-Property-Mobility Correlations

Abstract

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 2172558: Experimental Crystal Structure Determination

CCDC 2172559: Experimental Crystal Structure Determination

CCDC 2172557: Experimental Crystal Structure Determination

Cite this