Design and Synthesis of Annulated Benzothiadiazoles via Dithiolate Formation for Ambipolar Organic Semiconductors

Kolaczkowski, Matthew A.; Garzón-Ruiz, Andrés; Patel, Akash; Zhao, Zhiyuan; Guo, Yunlong; Navarro, Amparo; Liu, Yi

doi:10.1021/acsami.0c16056

Design and Synthesis of Annulated Benzothiadiazoles via Dithiolate Formation for Ambipolar Organic Semiconductors

Journal Article · Mon Nov 09 23:00:00 EST 2020 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.0c16056· OSTI ID:1833987

Kolaczkowski, Matthew A. ^[1]; ^[2]; Patel, Akash ^[1]; Zhao, Zhiyuan ^[3]; ^[3]; ^[4]; ^[5]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; Univ. of California, Berkeley, CA (United States)
Univ. de Castilla-La Mancha, Albacete (Spain)
Chinese Academy of Sciences (CAS), Beijing (China). Inst. of Chemistry
Univ. de Jaén (Spain)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry

Substituted 2,1,3-benzothiadiazole (BTD) is a widely used electron acceptor unit for functional organic semiconductors. Difluorination or annulation on the 5,6-position of the benzene ring is among the most adapted chemical modifications to tune the electronic properties, though each sees its own limitations in regulating the frontier orbital levels. Herein, a hitherto unreported 5,6-annulated BTD acceptor, denoted as ssBTD, is designed and synthesized by incorporating an electron-withdrawing 2-(1,3-dithiol-2-ylidene)malononitrile moiety via aromatic nucleophilic substitution of the 5,6-difluoroBTD (ffBTD) precursor. Unlike the other reported BTD annulation strategies, this modification leads to the simultaneous decrease in both frontier orbital energies, a welcoming feature for photovoltaic applications. Incorporation of ssBTD into conjugated polymers results in materials boasting broad light absorption, dramatic solvatochromic and thermochromic responses (>100 nm shift and a band gap difference of ~0.28 eV), and improved crystallinity in the solid state. Such physical properties are in accordance with the combined electron-withdrawing effect and significantly increased polarity associated with the ssBTD unit, as revealed by detailed theoretical studies. Furthermore, the thiolated ssBTD imbues the polymer with ambipolar charge transport property, in contrast to the ffBTD-based polymer, which transports holes only. While the low mobilities (10^-4 to 10^-5 cm² V^-1 s^-1) could be further optimized, detailed studies validate that the thioannulated BTD is a versatile electron-accepting unit for the design of functional stimuli-responsive optoelectronic materials.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1833987

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 47 Vol. 12; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Thin films
ambipolar
benzothiadiazole
conjugated polymers
dithiolate annulation
electron acceptor
molecules
organic semiconductor
polymers
solvatochromic
solvents

Design and Synthesis of Annulated Benzothiadiazoles via Dithiolate Formation for Ambipolar Organic Semiconductors

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