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Title: Materials Design via Optimized Intramolecular Noncovalent Interactions for High-Performance Organic Semiconductors

Journal Article · · Chemistry of Materials
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We report the design, synthesis, and implemention in semiconducting polymers of a novel head-to-head linkage containing the TRTOR (3-alkyl-3'-alkoxy-2,2'-bithiophene) donor subunit having a single strategically optimized, planarizing noncovalent S···O interaction. Diverse complementary thermal, optical, electrochemical, X-ray scattering, electrical, photovoltaic, and electron microscopic characterization techniques are applied to establish structure-property correlations in a TRTOR-based polymer series. In comparison to monomers having double S···O interactions, replacing one alkoxy substituent with a less electron-donating alkyl one yields TRTOR-based polymers with significantly depressed (0.2-0.3 eV) HOMOs. Furthermore, the weaker single S···O interaction and greater TRTOR steric encumberance enhances materials processability without sacrificing backbone planarity. From another perspective, TRTOR has comparable electronic properties to ring-fused 5Hdithieno[ 3,2-b:2',3'-d]pyran (DTP) subunits, but a centrosymmetric geometry which promotes a more compact and ordered structure than bulkier, axisymmetric DTP. Compared to monosubstituted TTOR (3-alkoxy-2,2'-bithiophene), alkylation at the TRTOR bithiophene 3-position enhances conjugation and polymer crystallinity with contracted π-π stacking. Grazing incidence wide-angle X-ray scattering (GIWAXS) data reveal that the greater steric hindrance and the weaker single S···O interaction are not detrimental to close packing and high crystallinity. As a proof of materials design, copolymerizing TRTOR with phthalimides yields copolymers with promising thin-film transistor mobility as high as 0.42 cm2/(V·s) and 6.3% power conversion efficiency in polymer solar cells, the highest of any phthalimide copolymers reported to date. The depressed TRTOR HOMOs imbue these polymers with substantially increased Ion/Ioff ratios and Voc’s versus analogous subunits with multiple electron donating, planarizing alkoxy substituents. Implementing a head-to-head linkage with an alkyl/alkoxy substitution pattern and a single S···O interaction is a promising strategy for organic electronics materials design.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Light Energy Activated Redox Processes (LEAP); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
DOE Contract Number:
AC02-06CH11357
OSTI ID:
1307653
Journal Information:
Chemistry of Materials, Vol. 28, Issue 7; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English

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  • Journal of the American Chemical Society, Vol. 132, Issue 22, p. 7595-7597 https://doi.org/10.1021/ja103275u
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Head-to-Head Linkage Containing Bithiophene-Based Polymeric Semiconductors for Highly Efficient Polymer Solar Cells journal September 2016
A Novel Naphtho[1,2- c :5,6- c′ ]Bis([1,2,5]Thiadiazole)-Based Narrow-Bandgap π-Conjugated Polymer with Power Conversion Efficiency Over 10% journal September 2016
Intramolecular Locked Dithioalkylbithiophene-Based Semiconductors for High-Performance Organic Field-Effect Transistors journal July 2017
Fluorinated Head-to-Head Dialkoxybithiophene: A New Electron-Donating Building Block for High-Performance Polymer Semiconductors journal December 2017
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Theory Meets Experiment for Noncovalent Complexes: The Puzzling Case of Pnicogen Interactions journal September 2018
A High Dielectric N-Type Small Molecular Acceptor Containing Oligoethyleneglycol Side-Chains for Organic Solar Cells journal January 2018
Building Blocks for High‐Efficiency Organic Photovoltaics: Interplay of Molecular, Crystal, and Electronic Properties in Post‐Fullerene ITIC Ensembles journal September 2019
Biphenyl Diimide Based Novel Blue Emitters with Aggregation‐Induced Blue‐Shifted Emission Characteristics journal August 2019
Donor-acceptor photovoltaic polymers based on 1,4-dithienyl-2,5-dialkoxybenzene with intramolecular noncovalent interactions journal January 2018
Efficient Nonfullerene Polymer Solar Cells Enabled by Small-Molecular Acceptors with a Decreased Fused-Ring Core journal March 2018
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Polymer semiconductors incorporating head-to-head linked 4-alkoxy-5-(3-alkylthiophen-2-yl)thiazole journal January 2018
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Why are S–F and S–O non-covalent interactions stabilising? journal January 2018
Probing non-covalent interactions driving molecular assembly in organo-electronic building blocks journal January 2019
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Synthesis and characterization of a semiconducting and solution-processable ruthenium-based polymetallayne journal January 2020
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