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A study of the degree of fluorination in regioregular poly(3-hexylthiophene)
Abstract
Here, we systematically varied the degree of fluorination along the backbone of a series of highly regioregular 3-hexylthiophene-based polymers, P3HT-50F, P3HT-33F and P3HT-25F, in which 50%, 33% and 25% of the thiophene units within the polymer chain contain fluorine atoms in the available 4-position. These materials were homopolymerized using the Kumada catalyst transfer polycondensation method from a set of mono-fluorinated bi-, ter- and quarterthiophenes, to ensure high polymer regioregularity and evenly-spaced fluorine atoms along the conjugated thiophene backbone. The monomers were obtained from a synthetic route consisting of iterative Migita-Stille couplings of fluorinated and non-fluorinated 3- hexylthiophenes. The effect of the fluorine atoms on both polymer structure and properties is presented, with supporting quantum mechanical calculations that rationalize the intrinsic conformation preferences of the three P3HT derivatives. P3HT-50F (M¯n = 34 kg/mol, 98.5% rr), P3HT-33F (M¯n = 46 kg/mol, 98% rr) and P3HT-25F (M¯n = 53 kg/mol, 95% rr) displayed HOMO levels of -5.34, -5.26 and -5.24 eV, bandgaps of 1.98, 1.98 and 1.97 eV, and average field-effect transistor hole mobilities of 4.5 × 10-3, 2.7 × 10-2, and 1.2 × 10-2 cm2 V-1s-1, respectively.
- Authors:
-
[2];
[1]
- Univ. Laval, Quebec City (Canada)
- Harvard Univ., Cambridge, MA (United States)
- Univ. of Waterloo, Waterloo, ON (Canada)
- Publication Date:
- Research Org.:
- Harvard Univ., Cambridge, MA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE)
- OSTI Identifier:
- 1336363
- Grant/Contract Number:
- SC0015959
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 50; Journal Issue: 1; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Blaskovits, J. Terence, Bura, Thomas, Beaupre, Serge, Lopez, Steven A., Roy, Carl, de Goes Soares, Julio, Oh, Adam, Quinn, Jesse, Li, Yuning, Aspuru-Guzik, Alan, and Leclerc, Mario. A study of the degree of fluorination in regioregular poly(3-hexylthiophene). United States: N. p., 2016.
Web. doi:10.1021/acs.macromol.6b02365.
Blaskovits, J. Terence, Bura, Thomas, Beaupre, Serge, Lopez, Steven A., Roy, Carl, de Goes Soares, Julio, Oh, Adam, Quinn, Jesse, Li, Yuning, Aspuru-Guzik, Alan, & Leclerc, Mario. A study of the degree of fluorination in regioregular poly(3-hexylthiophene). United States. https://doi.org/10.1021/acs.macromol.6b02365
Blaskovits, J. Terence, Bura, Thomas, Beaupre, Serge, Lopez, Steven A., Roy, Carl, de Goes Soares, Julio, Oh, Adam, Quinn, Jesse, Li, Yuning, Aspuru-Guzik, Alan, and Leclerc, Mario. 2016.
"A study of the degree of fluorination in regioregular poly(3-hexylthiophene)". United States. https://doi.org/10.1021/acs.macromol.6b02365. https://www.osti.gov/servlets/purl/1336363.
@article{osti_1336363,
title = {A study of the degree of fluorination in regioregular poly(3-hexylthiophene)},
author = {Blaskovits, J. Terence and Bura, Thomas and Beaupre, Serge and Lopez, Steven A. and Roy, Carl and de Goes Soares, Julio and Oh, Adam and Quinn, Jesse and Li, Yuning and Aspuru-Guzik, Alan and Leclerc, Mario},
abstractNote = {Here, we systematically varied the degree of fluorination along the backbone of a series of highly regioregular 3-hexylthiophene-based polymers, P3HT-50F, P3HT-33F and P3HT-25F, in which 50%, 33% and 25% of the thiophene units within the polymer chain contain fluorine atoms in the available 4-position. These materials were homopolymerized using the Kumada catalyst transfer polycondensation method from a set of mono-fluorinated bi-, ter- and quarterthiophenes, to ensure high polymer regioregularity and evenly-spaced fluorine atoms along the conjugated thiophene backbone. The monomers were obtained from a synthetic route consisting of iterative Migita-Stille couplings of fluorinated and non-fluorinated 3- hexylthiophenes. The effect of the fluorine atoms on both polymer structure and properties is presented, with supporting quantum mechanical calculations that rationalize the intrinsic conformation preferences of the three P3HT derivatives. P3HT-50F (M¯n = 34 kg/mol, 98.5% rr), P3HT-33F (M¯n = 46 kg/mol, 98% rr) and P3HT-25F (M¯n = 53 kg/mol, 95% rr) displayed HOMO levels of -5.34, -5.26 and -5.24 eV, bandgaps of 1.98, 1.98 and 1.97 eV, and average field-effect transistor hole mobilities of 4.5 × 10-3, 2.7 × 10-2, and 1.2 × 10-2 cm2 V-1s-1, respectively.},
doi = {10.1021/acs.macromol.6b02365},
url = {https://www.osti.gov/biblio/1336363},
journal = {Macromolecules},
issn = {0024-9297},
number = 1,
volume = 50,
place = {United States},
year = {Tue Dec 27 00:00:00 EST 2016},
month = {Tue Dec 27 00:00:00 EST 2016}
}
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Works referenced in this record:
Aryl−Perfluoroaryl Substituted Tetracene: Induction of Face-to-Face π−π Stacking and Enhancement of Charge Carrier Properties
journal, April 2011
- Okamoto, Toshihiro; Nakahara, Katsumasa; Saeki, Akinori
- Chemistry of Materials, Vol. 23, Issue 7
Fluorine Substituents Reduce Charge Recombination and Drive Structure and Morphology Development in Polymer Solar Cells
journal, January 2013
- Stuart, Andrew C.; Tumbleston, John R.; Zhou, Huaxing
- Journal of the American Chemical Society, Vol. 135, Issue 5
Polymer solar cells with enhanced open-circuit voltage and efficiency
journal, November 2009
- Chen, Hsiang-Yu; Hou, Jianhui; Zhang, Shaoqing
- Nature Photonics, Vol. 3, Issue 11, p. 649-653
Highly Efficient Solar Cell Polymers Developed via Fine-Tuning of Structural and Electronic Properties
journal, June 2009
- Liang, Yongye; Feng, Danqin; Wu, Yue
- Journal of the American Chemical Society, Vol. 131, Issue 22, p. 7792-7799
Ultimate efficiency of polymer/fullerene bulk heterojunction solar cells
journal, February 2006
- Koster, L. J. A.; Mihailetchi, V. D.; Blom, P. W. M.
- Applied Physics Letters, Vol. 88, Issue 9
Benzotriazole-Containing Planar Conjugated Polymers with Noncovalent Conformational Locks for Thermally Stable and Efficient Polymer Field-Effect Transistors
journal, March 2014
- Yum, Seungjib; An, Tae Kyu; Wang, Xiaowei
- Chemistry of Materials, Vol. 26, Issue 6
Semi-crystalline photovoltaic polymers with efficiency exceeding 9% in a ∼300 nm thick conventional single-cell device
journal, January 2014
- Nguyen, T. L.; Choi, H.; Ko, S. -J.
- Energy Environ. Sci., Vol. 7, Issue 9
Impact of Backbone Fluorination on π-Conjugated Polymers in Organic Photovoltaic Devices: A Review
journal, January 2016
- Leclerc, Nicolas; Chávez, Patricia; Ibraikulov, Olzhas
- Polymers, Vol. 8, Issue 1
Poly(3-fluorothiophene)
journal, August 1994
- El Kassmi, Ahmed; Fache, Fabienne; Lemaire, Marc
- Journal of Electroanalytical Chemistry, Vol. 373, Issue 1-2
Tetradecafluorosexithiophene: The First Perfluorinated Oligothiophene
journal, May 2001
- Sakamoto, Youichi; Komatsu, Shingo; Suzuki, Toshiyasu
- Journal of the American Chemical Society, Vol. 123, Issue 19
3-Fluoro-4-hexylthiophene as a Building Block for Tuning the Electronic Properties of Conjugated Polythiophenes
journal, February 2013
- Gohier, Frédéric; Frère, Pierre; Roncali, Jean
- The Journal of Organic Chemistry, Vol. 78, Issue 4
Functionalized Poly(3-hexylthiophene)s via Lithium–Bromine Exchange
journal, December 2014
- Koo, Byungjin; Sletten, Ellen M.; Swager, Timothy M.
- Macromolecules, Vol. 48, Issue 1
Influence of Backbone Fluorination in Regioregular Poly(3-alkyl-4-fluoro)thiophenes
journal, May 2015
- Fei, Zhuping; Boufflet, Pierre; Wood, Sebastian
- Journal of the American Chemical Society, Vol. 137, Issue 21
Systematic Fluorination of P3HT: Synthesis of P(3HT- co -3H4FT)s by Direct Arylation Polymerization, Characterization, and Device Performance in OPVs
journal, April 2016
- Homyak, Patrick D.; Liu, Yao; Harris, Jared D.
- Macromolecules, Vol. 49, Issue 8
On the effect of poly(3-hexylthiophene) regioregularity on inkjet printed organic solar cells
journal, January 2009
- Hoth, Claudia N.; Choulis, Stelios A.; Schilinsky, Pavel
- Journal of Materials Chemistry, Vol. 19, Issue 30
High Mobility Ambipolar Diketopyrrolopyrrole-Based Conjugated Polymer Synthesized Via Direct Arylation Polycondensation
journal, September 2015
- Gao, Yao; Zhang, Xiaojie; Tian, Hongkun
- Advanced Materials, Vol. 27, Issue 42
Direct (Hetero)arylation Polymerization: Trends and Perspectives
journal, July 2016
- Bura, Thomas; Blaskovits, J. Terence; Leclerc, Mario
- Journal of the American Chemical Society, Vol. 138, Issue 32
“Fibonacci’s Route” to Regioregular Oligo(3-hexylthiophene)s
journal, August 2013
- Koch, Felix P. V.; Smith, Paul; Heeney, Martin
- Journal of the American Chemical Society, Vol. 135, Issue 37
Highly Selective 5-Substitution of 3-Methylthiophene via Directed Lithiation
journal, February 2007
- Smith, Keith; Barratt, Mark Lewis
- The Journal of Organic Chemistry, Vol. 72, Issue 3
A Simple Method to Prepare Head-to-Tail Coupled, Regioregular Poly(3-alkylthiophenes) Using Grignard Metathesis
journal, March 1999
- Loewe, Robert S.; Khersonsky, Sonya M.; McCullough, Richard D.
- Advanced Materials, Vol. 11, Issue 3
Regioregular, Head-to-Tail Coupled Poly(3-alkylthiophenes) Made Easy by the GRIM Method: Investigation of the Reaction and the Origin of Regioselectivity
journal, May 2001
- Loewe, Robert S.; Ewbank, Paul C.; Liu, Jinsong
- Macromolecules, Vol. 34, Issue 13
Catalyst-Transfer Polycondensation. Mechanism of Ni-Catalyzed Chain-Growth Polymerization Leading to Well-Defined Poly(3-hexylthiophene)
journal, December 2005
- Miyakoshi, Ryo; Yokoyama, Akihiro; Yokozawa, Tsutomu
- Journal of the American Chemical Society, Vol. 127, Issue 49
Structural Analysis of Poly(3-hexylthiophene) Prepared via Direct Heteroarylation Polymerization
journal, May 2016
- Pouliot, Jean-Rémi; Wakioka, Masayuki; Ozawa, Fumiyuki
- Macromolecular Chemistry and Physics, Vol. 217, Issue 13
MALDI-ToF analysis of polythiophene: use of trans-2-[3-(4-t-butyl-phenyl)-2-methyl- 2-propenylidene]malononitrile-DCTB-as matrix
journal, March 2011
- Winter, Julien De; Deshayes, Gaëlle; Boon, Florian
- Journal of Mass Spectrometry, Vol. 46, Issue 3
Employing MALDI-MS on Poly(alkylthiophenes): Analysis of Molecular Weights, Molecular Weight Distributions, End-Group Structures, and End-Group Modifications
journal, September 1999
- Liu, Jinsong; Loewe, Robert S.; McCullough, Richard D.
- Macromolecules, Vol. 32, Issue 18
Ring Walking versus Trapping of Nickel(0) during Kumada Catalyst Transfer Polycondensation Using Externally Initiated Electron-Accepting Thiophene–Benzothiadiazole–Thiophene Precursors
journal, December 2011
- Komber, H.; Senkovskyy, V.; Tkachov, R.
- Macromolecules, Vol. 44, Issue 23
Determination of molecular weights and Mark–Houwink constants for soluble electronically conducting polymers
journal, December 1991
- Holdcroft, Steven
- Journal of Polymer Science Part B: Polymer Physics, Vol. 29, Issue 13
Kumada Catalyst-Transfer Polycondensation: Mechanism, Opportunities, and Challenges
journal, July 2011
- Kiriy, Anton; Senkovskyy, Volodymyr; Sommer, Michael
- Macromolecular Rapid Communications, Vol. 32, Issue 19
Tuning Mechanical and Optoelectrical Properties of Poly(3-hexylthiophene) through Systematic Regioregularity Control
journal, June 2015
- Kim, Jin-Seong; Kim, Jae-Han; Lee, Wonho
- Macromolecules, Vol. 48, Issue 13
Controlling Conformations of Conjugated Polymers and Small Molecules: The Role of Nonbonding Interactions
journal, May 2013
- Jackson, Nicholas E.; Savoie, Brett M.; Kohlstedt, Kevin L.
- Journal of the American Chemical Society, Vol. 135, Issue 28
Dramatic performance enhancement for large bandgap thick-film polymer solar cells introduced by a difluorinated donor unit
journal, July 2015
- Li, Zhengke; Lin, Haoran; Jiang, Kui
- Nano Energy, Vol. 15
On the Role of Single Regiodefects and Polydispersity in Regioregular Poly(3-hexylthiophene): Defect Distribution, Synthesis of Defect-Free Chains, and a Simple Model for the Determination of Crystallinity
journal, March 2012
- Kohn, Peter; Huettner, Sven; Komber, Hartmut
- Journal of the American Chemical Society, Vol. 134, Issue 10
Synthesis, Electronic Structure, Molecular Packing/Morphology Evolution, and Carrier Mobilities of Pure Oligo-/Poly(alkylthiophenes)
journal, December 2012
- Zhang, Lei; Colella, Nicholas S.; Liu, Feng
- Journal of the American Chemical Society, Vol. 135, Issue 2
The Chemistry of Conducting Polythiophenes
journal, January 1998
- McCullough, Richard D.
- Advanced Materials, Vol. 10, Issue 2, p. 93-116
Effect of Molecular Weight on Spectroscopic and Spectroelectrochemical Properties of Regioregular Poly(3-hexylthiophene)
journal, July 1998
- Trznadel, Miroslaw; Pron, Adam; Zagorska, Malgorzata
- Macromolecules, Vol. 31, Issue 15
Works referencing / citing this record:
3,4‐Dicyanothiophene—a Versatile Building Block for Efficient Nonfullerene Polymer Solar Cells
journal, March 2020
- Zhang, Bo; Yu, Yonggao; Zhou, Jiadong
- Advanced Energy Materials, Vol. 10, Issue 12
Tuning the optoelectronic properties of oligothiophenes for solar cell applications by varying the number of cyano and fluoro substituents for solar cell applications: A theoretical study
journal, December 2019
- Franco, Francisco C.
- Journal of Chemical Research, Vol. 44, Issue 3-4
Organic and Organometallic Fluorinated Materials for Electronics and Optoelectronics: A Survey on Recent Research: Organic and Organometallic Fluorinated Materials for Electronics and Optoelectronics: A Survey on Recent Research
journal, June 2018
- Ragni, Roberta; Punzi, Angela; Babudri, Francesco
- European Journal of Organic Chemistry, Vol. 2018, Issue 27-28
CH Activation as a Shortcut to Conjugated Polymer Synthesis
journal, September 2018
- Blaskovits, J. Terence; Leclerc, Mario
- Macromolecular Rapid Communications, Vol. 40, Issue 1
Fluorination vs. chlorination: a case study on high performance organic photovoltaic materials
journal, June 2018
- Zhang, Yun; Yao, Huifeng; Zhang, Shaoqing
- Science China Chemistry, Vol. 61, Issue 10
Diversifying Cross-Coupling Strategies, Catalysts and Monomers for the Controlled Synthesis of Conjugated Polymers
journal, June 2018
- Baker, Matthew A.; Tsai, Chia-Hua; Noonan, Kevin J. T.
- Chemistry - A European Journal, Vol. 24, Issue 50