Influence of the Carboxylic Acid Additive Structure on the Properties of Poly(3-hexylthiophene) Prepared via Direct Arylation Polymerization (DArP)
Abstract
Carboxylic acids are known to have a profound effect on the rate of direct arylation. Despite this, little attention has been paid to them as additives for direct arylation polymerization (DArP). Here we report the influence of the carboxylic acid chemical structure on the properties of poly(3-hexylthiophene) (P3HT) prepared via DArP. We study the effect that acid pKa, steric bulk, and backbone cyclization have on the reactivity of the DArP catalytic system. We found that pKa values do not correlate with DArP reactivity in the pKa range of 4.76–5.05. The increase of acid size in the classes of linear, secondary, and tertiary acids leads to a continuous increase in polymer yield and molecular weight, whereas for the case of cyclic secondary acids the trend is reversed and a decrease of acid size leads to an increase in polymer yield and molecular weight in an alternating (zigzag) fashion depending on whether the acid contains an even or odd number of carbons. Here, a profound enhancement of reactivity was found for the case of the smallest cyclopropanecarboxylic acid, which yields P3HT with remarkably high molecular weights (Mn 33.4 kDa and Mw 207.1 kDa), which is expected to benefit the development of directmore »
- Authors:
-
- Univ. of Southern California, Los Angeles, CA (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Energy Nanoscience (CEN)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1369887
- Grant/Contract Number:
- SC0001013
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 48; Journal Issue: 3; Related Information: CEN partners with University of Southern California (lead); University of Illinois, Urbana-Champaign; University of Michigan; University of Virginia; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Organic acids; Organic polymers; Chemical structure; Reactivity; Polymers
Citation Formats
Rudenko, Andrey E., and Thompson, Barry C. Influence of the Carboxylic Acid Additive Structure on the Properties of Poly(3-hexylthiophene) Prepared via Direct Arylation Polymerization (DArP). United States: N. p., 2015.
Web. doi:10.1021/ma502131k.
Rudenko, Andrey E., & Thompson, Barry C. Influence of the Carboxylic Acid Additive Structure on the Properties of Poly(3-hexylthiophene) Prepared via Direct Arylation Polymerization (DArP). United States. https://doi.org/10.1021/ma502131k
Rudenko, Andrey E., and Thompson, Barry C. Thu .
"Influence of the Carboxylic Acid Additive Structure on the Properties of Poly(3-hexylthiophene) Prepared via Direct Arylation Polymerization (DArP)". United States. https://doi.org/10.1021/ma502131k. https://www.osti.gov/servlets/purl/1369887.
@article{osti_1369887,
title = {Influence of the Carboxylic Acid Additive Structure on the Properties of Poly(3-hexylthiophene) Prepared via Direct Arylation Polymerization (DArP)},
author = {Rudenko, Andrey E. and Thompson, Barry C.},
abstractNote = {Carboxylic acids are known to have a profound effect on the rate of direct arylation. Despite this, little attention has been paid to them as additives for direct arylation polymerization (DArP). Here we report the influence of the carboxylic acid chemical structure on the properties of poly(3-hexylthiophene) (P3HT) prepared via DArP. We study the effect that acid pKa, steric bulk, and backbone cyclization have on the reactivity of the DArP catalytic system. We found that pKa values do not correlate with DArP reactivity in the pKa range of 4.76–5.05. The increase of acid size in the classes of linear, secondary, and tertiary acids leads to a continuous increase in polymer yield and molecular weight, whereas for the case of cyclic secondary acids the trend is reversed and a decrease of acid size leads to an increase in polymer yield and molecular weight in an alternating (zigzag) fashion depending on whether the acid contains an even or odd number of carbons. Here, a profound enhancement of reactivity was found for the case of the smallest cyclopropanecarboxylic acid, which yields P3HT with remarkably high molecular weights (Mn 33.4 kDa and Mw 207.1 kDa), which is expected to benefit the development of direct arylation protocols for inherently less reactive substrates.},
doi = {10.1021/ma502131k},
journal = {Macromolecules},
number = 3,
volume = 48,
place = {United States},
year = {Thu Jan 29 00:00:00 EST 2015},
month = {Thu Jan 29 00:00:00 EST 2015}
}
Web of Science
Works referenced in this record:
Carboxylate-Assisted Transition-Metal-Catalyzed C−H Bond Functionalizations: Mechanism and Scope
journal, March 2011
- Ackermann, Lutz
- Chemical Reviews, Vol. 111, Issue 3
Aryl−Aryl Bond Formation by Transition-Metal-Catalyzed Direct Arylation
journal, January 2007
- Alberico, Dino; Scott, Mark E.; Lautens, Mark
- Chemical Reviews, Vol. 107, Issue 1
Palladium-Catalyzed Benzene Arylation: Incorporation of Catalytic Pivalic Acid as a Proton Shuttle and a Key Element in Catalyst Design
journal, December 2006
- Lafrance, Marc; Fagnou, Keith
- Journal of the American Chemical Society, Vol. 128, Issue 51
Analysis of the Concerted Metalation-Deprotonation Mechanism in Palladium-Catalyzed Direct Arylation Across a Broad Range of Aromatic Substrates
journal, August 2008
- Gorelsky, Serge I.; Lapointe, David; Fagnou, Keith
- Journal of the American Chemical Society, Vol. 130, Issue 33
Analysis of the Palladium-Catalyzed (Aromatic)C–H Bond Metalation–Deprotonation Mechanism Spanning the Entire Spectrum of Arenes
journal, December 2011
- Gorelsky, Serge I.; Lapointe, David; Fagnou, Keith
- The Journal of Organic Chemistry, Vol. 77, Issue 1
Optimization of direct arylation polymerization (DArP) through the identification and control of defects in polymer structure
journal, June 2014
- Rudenko, Andrey E.; Thompson, Barry C.
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 53, Issue 2
C–H Arylation Reaction: Atom Efficient and Greener Syntheses of π-Conjugated Small Molecules and Macromolecules for Organic Electronic Materials
journal, August 2013
- Okamoto, Ken; Zhang, Junxiang; Housekeeper, Jeremy B.
- Macromolecules, Vol. 46, Issue 20
Direct Arylation Polymerization: A Green, Streamlining Synthetic Approach to π -conjugated Polymers
journal, May 2013
- Wang, Kai; Wang, Mingfeng
- Current Organic Chemistry, Vol. 17, Issue 9
Direct arylation polycondensation as simplified alternative for the synthesis of conjugated (co)polymers
journal, December 2013
- Kowalski, S.; Allard, S.; Zilberberg, K.
- Progress in Polymer Science, Vol. 38, Issue 12
Semiconducting Polymers Prepared by Direct Arylation Polycondensation
journal, March 2012
- Facchetti, Antonio; Vaccaro, Luigi; Marrocchi, Assunta
- Angewandte Chemie International Edition, Vol. 51, Issue 15
Semi-random P3HT analogs via direct arylation polymerization
journal, June 2012
- Rudenko, Andrey E.; Wiley, Calvin A.; Stone, Shiloh M.
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 50, Issue 18, p. 3691-3697
Palladium-Catalyzed Dehydrohalogenative Polycondensation of 2-Bromo-3-hexylthiophene: An Efficient Approach to Head-to-Tail Poly(3-hexylthiophene)
journal, August 2010
- Wang, Qifeng; Takita, Ryo; Kikuzaki, Yuuta
- Journal of the American Chemical Society, Vol. 132, Issue 33
Direct (Hetero)Arylation: A New Tool for Polymer Chemists
journal, April 2013
- Mercier, Lauren G.; Leclerc, Mario
- Accounts of Chemical Research, Vol. 46, Issue 7
Microwave-Assisted Polycondensation via Direct Arylation of 3,4-Ethylenedioxythiophene with 9,9-Dioctyl-2,7-dibromofluorene
journal, May 2013
- Choi, Seong Jib; Kuwabara, Junpei; Kanbara, Takaki
- ACS Sustainable Chemistry & Engineering, Vol. 1, Issue 8
A Highly Efficient Catalytic System for Polycondensation of 2,7-Dibromo-9,9-dioctylfluorene and 1,2,4,5-Tetrafluorobenzene via Direct Arylation
journal, December 2012
- Wakioka, Masayuki; Kitano, Yutaro; Ozawa, Fumiyuki
- Macromolecules, Vol. 46, Issue 2
Optimization of direct arylation polymerization conditions for the synthesis of poly(3-hexylthiophene)
journal, March 2013
- Rudenko, Andrey E.; Wiley, Calvin A.; Tannaci, John F.
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 51, Issue 12
Relation between absorption and crystallinity of poly(3-hexylthiophene)/fullerene films for plastic solar cells
journal, February 2006
- Zhokhavets, Uladzimir; Erb, Tobias; Gobsch, Gerhard
- Chemical Physics Letters, Vol. 418, Issue 4-6
“Semi-Random” Multichromophoric rr-P3HT Analogues for Solar Photon Harvesting
journal, March 2011
- Burkhart, Beate; Khlyabich, Petr P.; Cakir Canak, Tuba
- Macromolecules, Vol. 44, Issue 6
Neo acids: Synthetic highly branched organic acids
journal, April 1978
- Fefer, M.
- Journal of the American Oil Chemists' Society, Vol. 55, Issue 4
Neo acids chemistry and applications
journal, January 1968
- Fefer, M.; Rutkowski, A. J.
- Journal of the American Oil Chemists' Society, Vol. 45, Issue 1
Regiocontrolled Synthesis of Poly(3-alkylthiophenes) Mediated by Rieke Zinc: Their Characterization and Solid-State Properties
journal, January 1995
- Chen, Tian-An; Wu, Xiaoming; Rieke, Reuben D.
- Journal of the American Chemical Society, Vol. 117, Issue 1, p. 233-244
Influence of β-linkages on the morphology and performance of DArP P3HT–PC 61 BM solar cells
journal, December 2013
- Rudenko, Andrey E.; Latif, Alia A.; Thompson, Barry C.
- Nanotechnology, Vol. 25, Issue 1
Thiophene based hyperbranched polymers with tunable branching using direct arylation methods
journal, January 2013
- Okamoto, Ken; Housekeeper, Jeremy B.; Michael, Forrest E.
- Polymer Chemistry, Vol. 4, Issue 12
Origins of regioselectivity of the palladium-catalyzed (aromatic)CH bond metalation–deprotonation
journal, January 2013
- Gorelsky, Serge I.
- Coordination Chemistry Reviews, Vol. 257, Issue 1
Ru-catalyzed site-selective direct arylation polycondensation via ortho -metalation of pyrrole derivative
journal, March 2014
- Kanbara, T.; Kuwabara, J.; Lu, W.
- IOP Conference Series: Materials Science and Engineering, Vol. 54
Detailed Optimization of Polycondensation Reaction via Direct C-H Arylation of Ethylenedioxythiophene
journal, October 2012
- Yamazaki, Koutarou; Kuwabara, Junpei; Kanbara, Takaki
- Macromolecular Rapid Communications, Vol. 34, Issue 1, p. 69-73
General approach to measurements of pK a differences by 13C NMR spectroscopy
journal, January 1996
- Pehk, Tonis; Kiirend, Ene; Lippmaa, Endel
- Journal of the Chemical Society, Perkin Transactions 2, Issue 11
Real time measurement of the structural change in P3HT:PCBM thin films and the relation with device performance in OPV cells
conference, August 2009
- Kim, Hyo Jung; Lee, Hyun Hwi; Kim, Jang-Joo
- SPIE Photonic Devices + Applications, SPIE Proceedings
The Influence of Interchain Branches on Solid State Packing, Hole Mobility and Photovoltaic Properties of Poly(3-hexylthiophene) (P3HT)
journal, September 2007
- Tu, Guoli; Bilge, Askin; Adamczyk, Sylwia
- Macromolecular Rapid Communications, Vol. 28, Issue 17
Direct Arylation of 2-Methylthiophene with Isolated [PdAr(μ-O 2 CR)(PPh 3 )] n Complexes: Kinetics and Mechanism
journal, June 2012
- Wakioka, Masayuki; Nakamura, Yuki; Wang, Qifeng
- Organometallics, Vol. 31, Issue 13
Computational and Experimental Studies of Methyl Group Exchange between Palladium(II) Centers
journal, April 2010
- Remy, Matthew S.; Cundari, Thomas R.; Sanford, Melanie S.
- Organometallics, Vol. 29, Issue 7
Thermal quantities of some cycloparaffins. Part III. results of measurements
journal, January 1952
- Kaarsemaker, Sj.; Coops, J.
- Recueil des Travaux Chimiques des Pays-Bas, Vol. 71, Issue 3
Zur Kenntnis des Kohlenstoffringes. 49. Mitteilung. Vielgliedrige Cyclanole und Cyclanol-acetate
journal, February 1949
- Kobelt, Margrit; Barman, P.; Prelog, V.
- Helvetica Chimica Acta, Vol. 32, Issue 1
C 13 and H 1 Nuclear Magnetic Resonance Spectra of Cycloalkanes
journal, May 1964
- Burke, John J.; Lauterbur, Paul C.
- Journal of the American Chemical Society, Vol. 86, Issue 9
Works referencing / citing this record:
Direct arylation polymerization toward ultra-low bandgap poly(thienoisoindigo- alt -diketopyrrolepyrrole) conjugated polymers: The effect of β-protection on the polymerization and properties of the polymers
journal, July 2017
- Wang, Kai; Huang, Jing; Ko, Jieun
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 55, Issue 19
Current methodologies for a sustainable approach to π-conjugated organic semiconductors
journal, January 2016
- Marrocchi, Assunta; Facchetti, Antonio; Lanari, Daniela
- Energy & Environmental Science, Vol. 9, Issue 3
Steric Effect of Carboxylate Ligands on Pd-Catalyzed Intramolecular C(sp 2 )-H and C(sp 3 )-H Arylation Reactions
journal, June 2018
- Tanji, Yutaka; Mitsutake, Naoya; Fujihara, Tetsuaki
- Angewandte Chemie International Edition, Vol. 57, Issue 32
Synthesis of D- π -A- π type benzodithiophene-quinoxaline copolymers by direct arylation and their application in organic solar cells
journal, April 2018
- Zimmermann, Diana; Sprau, Christian; Schröder, Jonas
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 56, Issue 13
Steric Effect of Carboxylate Ligands on Pd-Catalyzed Intramolecular C(sp 2 )-H and C(sp 3 )-H Arylation Reactions
journal, June 2018
- Tanji, Yutaka; Mitsutake, Naoya; Fujihara, Tetsuaki
- Angewandte Chemie, Vol. 130, Issue 32
Direct heteroarylation polymerization: guidelines for defect-free conjugated polymers
journal, January 2017
- Bura, Thomas; Beaupré, Serge; Légaré, Marc-André
- Chemical Science, Vol. 8, Issue 5
Influence of an ester directing-group on defect formation in the synthesis of conjugated polymers via direct arylation polymerization (DArP) using sustainable solvents
journal, January 2019
- Pankow, Robert M.; Ye, Liwei; Thompson, Barry C.
- Polymer Chemistry, Vol. 10, Issue 33
Exploration of the Direct Arylation Polymerization Method for the Practical Application of Conjugated Materials: Synthetic Scale-Up, Solar Cell Performance, and Cost Analyses
journal, October 2018
- Pappenfus, Ted M.; Almyahi, Furqan; Cooling, Nathan A.
- Macromolecular Chemistry and Physics, Vol. 219, Issue 21
The Direct Arylation Polymerization (DArP) of Well-Defined Alternating Copolymers Based On 5,6-Dicyano[2,1,3]benzothiadiazole (DCBT)
journal, June 2018
- Shi, Qinqin; Tatum, Wesley; Zhang, Junxiang
- Asian Journal of Organic Chemistry, Vol. 7, Issue 7
In vitro and In silico Studies on the Base Effect in Palladium‐Catalyzed Direct Arylation
journal, January 2020
- Lai, Yu‐Ying; Yang, Hau‐Ren; Lee, Hao‐Ting
- Asian Journal of Organic Chemistry, Vol. 9, Issue 2
Recent Developments in C–H Activation for Materials Science in the Center for Selective C–H Activation
journal, April 2018
- Zhang, Junxiang; Kang, Lauren; Parker, Timothy
- Molecules, Vol. 23, Issue 4