Monofluorination of Naphthyls Promotes the Cofacial π–π Stacking and Increases the Electron Mobility of Non-Planar Zinc(II) Complexes of Di(naphthylethynyl)azadipyrromethene
Abstract
The homoleptic zinc(II) complex of [2,8-di(1-naphthylethynyl) 3,7-diphenyl 1,9-(4-hexylphenyl)azadipyrromethene (ZnL2)2] is a promising non-planar non-fullerene acceptor for organic photovoltaic applications, but it has a relatively low electron mobility that may limit its performance. Here, we explored the fluorination of peripheral aryl groups to increase intermolecular cofacial π–π stacking interactions, which are desirable for electron transport. Here complexes with fluorine on the distal phenyls [Zn(1F-L2)2], on the naphthyls [Zn(2F-L2)2], and on both [Zn(3F-L2)2] were synthesized and characterized. All three complexes had similar optical and electrochemical properties. The crystal packing structure of Zn(2F-L2)2 and Zn(3F-L2)2 revealed cofacial parallel-displaced π–π stacking between the fluorinated 1-naphthylethynyl groups. Such a cofacial orientation was not observed in Zn(L2)2 crystals, suggesting that fluorination of the naphthyl groups promotes the cofacial π–π stacking orientation. The hole mobility increased from 1.0 × 10–4 cm2 V–1 s–1 for Zn(L2)2 to 0.8–1.0 × 10–3 cm2 V–1 s–1 for the fluorinated complexes. Fluorination on the naphthyl groups increased the electron mobility from 4.2 × 10–5 cm2 V–1 s–1 for Zn(L2)2 and Zn(1F-L2)2 to 2.0 × 10–4 cm2 V–1 s–1 for Zn(2F-L2)2 and Zn(3F-L2)2, consistent with cofacial π–π stacking being favorable for electron transport. The three complexes were tested in OPVs using regioregular poly(3-hexylthiophene)more »
- Authors:
-
[1];
[1];
[1];
[1];
[2];
[1];
[1]
- Case Western Reserve Univ., Cleveland, OH (United States)
- Univ. of California, San Diego, La Jolla, CA (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1889631
- Report Number(s):
- BNL-223441-2022-JAAM
Journal ID: ISSN 1932-7447
- Grant/Contract Number:
- SC0012704; CHEM 1904868; MRI-0821515; MRI-1334048
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 126; Journal Issue: 15; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; charge transport; halogenation; mobility; molecules; organic polymers
Citation Formats
Zhao, Muyuan, Jimenez, Jayvic C., Wang, Chunlai, Rui, Guanchun, Ma, Tingrui, Lu, Chenwei, Rheingold, Arnold L., Li, Ruipeng, Zhu, Lei, and Sauvé, Geneviève. Monofluorination of Naphthyls Promotes the Cofacial π–π Stacking and Increases the Electron Mobility of Non-Planar Zinc(II) Complexes of Di(naphthylethynyl)azadipyrromethene. United States: N. p., 2022.
Web. doi:10.1021/acs.jpcc.1c09734.
Zhao, Muyuan, Jimenez, Jayvic C., Wang, Chunlai, Rui, Guanchun, Ma, Tingrui, Lu, Chenwei, Rheingold, Arnold L., Li, Ruipeng, Zhu, Lei, & Sauvé, Geneviève. Monofluorination of Naphthyls Promotes the Cofacial π–π Stacking and Increases the Electron Mobility of Non-Planar Zinc(II) Complexes of Di(naphthylethynyl)azadipyrromethene. United States. https://doi.org/10.1021/acs.jpcc.1c09734
Zhao, Muyuan, Jimenez, Jayvic C., Wang, Chunlai, Rui, Guanchun, Ma, Tingrui, Lu, Chenwei, Rheingold, Arnold L., Li, Ruipeng, Zhu, Lei, and Sauvé, Geneviève. Wed .
"Monofluorination of Naphthyls Promotes the Cofacial π–π Stacking and Increases the Electron Mobility of Non-Planar Zinc(II) Complexes of Di(naphthylethynyl)azadipyrromethene". United States. https://doi.org/10.1021/acs.jpcc.1c09734. https://www.osti.gov/servlets/purl/1889631.
@article{osti_1889631,
title = {Monofluorination of Naphthyls Promotes the Cofacial π–π Stacking and Increases the Electron Mobility of Non-Planar Zinc(II) Complexes of Di(naphthylethynyl)azadipyrromethene},
author = {Zhao, Muyuan and Jimenez, Jayvic C. and Wang, Chunlai and Rui, Guanchun and Ma, Tingrui and Lu, Chenwei and Rheingold, Arnold L. and Li, Ruipeng and Zhu, Lei and Sauvé, Geneviève},
abstractNote = {The homoleptic zinc(II) complex of [2,8-di(1-naphthylethynyl) 3,7-diphenyl 1,9-(4-hexylphenyl)azadipyrromethene (ZnL2)2] is a promising non-planar non-fullerene acceptor for organic photovoltaic applications, but it has a relatively low electron mobility that may limit its performance. Here, we explored the fluorination of peripheral aryl groups to increase intermolecular cofacial π–π stacking interactions, which are desirable for electron transport. Here complexes with fluorine on the distal phenyls [Zn(1F-L2)2], on the naphthyls [Zn(2F-L2)2], and on both [Zn(3F-L2)2] were synthesized and characterized. All three complexes had similar optical and electrochemical properties. The crystal packing structure of Zn(2F-L2)2 and Zn(3F-L2)2 revealed cofacial parallel-displaced π–π stacking between the fluorinated 1-naphthylethynyl groups. Such a cofacial orientation was not observed in Zn(L2)2 crystals, suggesting that fluorination of the naphthyl groups promotes the cofacial π–π stacking orientation. The hole mobility increased from 1.0 × 10–4 cm2 V–1 s–1 for Zn(L2)2 to 0.8–1.0 × 10–3 cm2 V–1 s–1 for the fluorinated complexes. Fluorination on the naphthyl groups increased the electron mobility from 4.2 × 10–5 cm2 V–1 s–1 for Zn(L2)2 and Zn(1F-L2)2 to 2.0 × 10–4 cm2 V–1 s–1 for Zn(2F-L2)2 and Zn(3F-L2)2, consistent with cofacial π–π stacking being favorable for electron transport. The three complexes were tested in OPVs using regioregular poly(3-hexylthiophene) (P3HT) as the p-type material, and the best power conversion efficiencies were 5.2, 5.4, and 5.8% for Zn(2F-L2)2, Zn(1F-L2)2, and Zn(3F-L2)2, respectively, compared to 5.5% for Zn(L2)2. The fluorination combination found in Zn(3F-L2)2 resulted in the best device performance. This study points to a viable strategy to increase the electron mobility and performance of non-planar zinc(II) complexes of azadipyrromethene.},
doi = {10.1021/acs.jpcc.1c09734},
journal = {Journal of Physical Chemistry. C},
number = 15,
volume = 126,
place = {United States},
year = {Wed Apr 06 00:00:00 EDT 2022},
month = {Wed Apr 06 00:00:00 EDT 2022}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Design, synthesis and photophysical studies of dipyrromethene-based materials: insights into their applications in organic photovoltaic devices
journal, January 2014
- Bessette, André; Hanan, Garry S.
- Chem. Soc. Rev., Vol. 43, Issue 10
Polymer-Fullerene Bulk-Heterojunction Solar Cells
journal, August 2010
- Brabec, Christoph J.; Gowrisanker, Srinivas; Halls, Jonathan J. M.
- Advanced Materials, Vol. 22, Issue 34
BODIPY Dyes and Their Derivatives: Syntheses and Spectroscopic Properties
journal, November 2007
- Loudet, Aurore; Burgess, Kevin
- Chemical Reviews, Vol. 107, Issue 11
The Curious Case of Fluorination of Conjugated Polymers for Solar Cells
journal, August 2017
- Zhang, Qianqian; Kelly, Mary Allison; Bauer, Nicole
- Accounts of Chemical Research, Vol. 50, Issue 9
Fused-Ring Electron Acceptors for Photovoltaics and Beyond
journal, December 2020
- Wang, Jiayu; Zhan, Xiaowei
- Accounts of Chemical Research, Vol. 54, Issue 1
8.4% efficient fullerene-free organic solar cells exploiting long-range exciton energy transfer
journal, March 2014
- Cnops, Kjell; Rand, Barry P.; Cheyns, David
- Nature Communications, Vol. 5, Issue 1
Azadipyrromethene-Based Zn(II) Complexes as Nonplanar Conjugated Electron Acceptors for Organic Photovoltaics
journal, July 2014
- Mao, Zhenghao; Senevirathna, Wasana; Liao, Jia-Yu
- Advanced Materials, Vol. 26, Issue 36
Synthesis and characterization of fluorinated azadipyrromethene complexes as acceptors for organic photovoltaics
journal, January 2016
- Etheridge, Forrest S.; Fernando, Roshan J.; Pejić, Sandra
- Beilstein Journal of Organic Chemistry, Vol. 12
The rotational spectrum, structure and dynamics of a benzene dimer
journal, March 1993
- Arunan, E.; Gutowsky, H. S.
- The Journal of Chemical Physics, Vol. 98, Issue 5
Recent progress of PM6:Y6-based high efficiency organic solar cells
journal, April 2021
- Wen, Zhen-Chuan; Yin, Hang; Hao, Xiao-Tao
- Surfaces and Interfaces, Vol. 23
Electronic Structures and Charge Transport of Stacked Annelated β-Trithiophenes
journal, November 2010
- Liu, Hongguang; Kang, Sunwoo; Lee, Jin Yong
- The Journal of Physical Chemistry B, Vol. 115, Issue 18
Recent advances, challenges and prospects in ternary organic solar cells
journal, January 2021
- Zhao, Congcong; Wang, Jiuxing; Zhao, Xuanyi
- Nanoscale, Vol. 13, Issue 4
Simple Non‐Fused Electron Acceptors Leading to Efficient Organic Photovoltaics
journal, May 2021
- Wen, Tian‐Jiao; Liu, Zhi‐Xi; Chen, Zeng
- Angewandte Chemie International Edition, Vol. 60, Issue 23
Analyzing the efficiency, stability and cost potential for fullerene-free organic photovoltaics in one figure of merit
journal, January 2018
- Li, Ning; McCulloch, Iain; Brabec, Christoph J.
- Energy & Environmental Science, Vol. 11, Issue 6
Achieving over 10 % Efficiency in Poly(3‐hexylthiophene)‐Based Organic Solar Cells via Solid Additives
journal, June 2021
- Yang, Chenyi; Yu, Runnan; Liu, Chenyu
- ChemSusChem, Vol. 14, Issue 17
Effect of molecular packing of zinc(II) porphyrins on the performance of field-effect transistors
journal, November 2014
- Hoang, Mai Ha; Ngo, Trinh Tung; Nguyen, Duc Nghia
- Advances in Natural Sciences: Nanoscience and Nanotechnology, Vol. 5, Issue 4
Crystallography, Morphology, Electronic Structure, and Transport in Non-Fullerene/Non-Indacenodithienothiophene Polymer:Y6 Solar Cells
journal, July 2020
- Zhu, Weigang; Spencer, Austin P.; Mukherjee, Subhrangsu
- Journal of the American Chemical Society, Vol. 142, Issue 34
Substituent Effects in the Benzene Dimer are Due to Direct Interactions of the Substituents with the Unsubstituted Benzene
journal, August 2008
- Wheeler, Steven E.; Houk, K. N.
- Journal of the American Chemical Society, Vol. 130, Issue 33
fac-Tricarbonyl Rhenium(I) Azadipyrromethene Complexes
journal, September 2009
- Partyka, David V.; Deligonul, Nihal; Washington, Marlena P.
- Organometallics, Vol. 28, Issue 20
Azadipyrromethenes: from traditional dye chemistry to leading edge applications
journal, January 2016
- Ge, Yuan; O'Shea, Donal F.
- Chemical Society Reviews, Vol. 45, Issue 14
Density Functional Theory Study Predicts Low Reorganization Energies for Azadipyrromethene-Based Metal Complexes
journal, February 2014
- Senevirathna, Wasana; Daddario, Cassie M.; Sauvé, Geneviève
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 5
Synthesis of Fullerene Derivatives for the Application to Organic Photovoltaic Cell and n-Channel Organic Thin-Film Transistors
journal, February 2016
- Yun, Jin-Mun; Kim, Dong-Yu; Noh, Yong-Young
- Science of Advanced Materials, Vol. 8, Issue 2
Air-stable and high-performance organic field-effect transistors based on ordered, large-domain phthalocyanine copper thin film
journal, December 2015
- Qian, Chuan; Sun, Jia; Zhang, Lei
- Synthetic Metals, Vol. 210
Substituent Effects in π−π Interactions: Sandwich and T-Shaped Configurations
journal, June 2004
- Sinnokrot, Mutasem Omar; Sherrill, C. David
- Journal of the American Chemical Society, Vol. 126, Issue 24
Enhancing charge mobilities in organic semiconductors by selective fluorination: a design approach based on a quantum mechanical perspective
journal, January 2017
- Maiti, Buddhadev; Schubert, Alexander; Sarkar, Sunandan
- Chem. Sci., Vol. 8, Issue 10
Pinpoint-Fluorinated Phenacenes: New Synthesis and Solubility Enhancement Strategies
journal, February 2015
- Fuchibe, Kohei; Morikawa, Toshiyuki; Shigeno, Kento
- Organic Letters, Vol. 17, Issue 5
The role of chemical design in the performance of organic semiconductors
journal, January 2020
- Bronstein, Hugo; Nielsen, Christian B.; Schroeder, Bob C.
- Nature Reviews Chemistry, Vol. 4, Issue 2
Organic and Polymeric Semiconductors Enhanced by Noncovalent Conformational Locks
journal, July 2017
- Huang, Hui; Yang, Lei; Facchetti, Antonio
- Chemical Reviews, Vol. 117, Issue 15
The Active Layer Morphology of Organic Solar Cells Probed with Grazing Incidence Scattering Techniques
journal, February 2014
- Müller-Buschbaum, Peter
- Advanced Materials, Vol. 26, Issue 46
A zinc( ii ) complex of di(naphthylethynyl)azadipyrromethene with low synthetic complexity leads to OPV with high industrial accessibility
journal, January 2019
- Wang, Chunlai; Wei, Peiran; Ngai, Jenner H. L.
- Journal of Materials Chemistry A, Vol. 7, Issue 42
Effect of traps on the performance of bulk heterojunction organic solar cells
journal, December 2007
- Mandoc, M. M.; Kooistra, F. B.; Hummelen, J. C.
- Applied Physics Letters, Vol. 91, Issue 26
“Conformation Locked” Strong Electron-Deficient Poly( p -Phenylene Vinylene) Derivatives for Ambient-Stable n-Type Field-Effect Transistors: Synthesis, Properties, and Effects of Fluorine Substitution Position
journal, January 2014
- Lei, Ting; Xia, Xin; Wang, Jie-Yu
- Journal of the American Chemical Society, Vol. 136, Issue 5
Organic solar cells based on a novel infrared absorbing aza-bodipy dye
journal, April 2012
- Mueller, Toni; Gresser, Roland; Leo, Karl
- Solar Energy Materials and Solar Cells, Vol. 99
Porphyrins and BODIPY as Building Blocks for Efficient Donor Materials in Bulk Heterojunction Solar Cells
journal, October 2017
- Bucher, Léo; Desbois, Nicolas; Harvey, Pierre D.
- Solar RRL, Vol. 1, Issue 12
Quantitative Determination of Organic Semiconductor Microstructure from the Molecular to Device Scale
journal, June 2012
- Rivnay, Jonathan; Mannsfeld, Stefan C. B.; Miller, Chad E.
- Chemical Reviews, Vol. 112, Issue 10
Electronic sensing of vapors with organic transistors
journal, April 2001
- Crone, B.; Dodabalapur, A.; Gelperin, A.
- Applied Physics Letters, Vol. 78, Issue 15
“All That Glisters Is Not Gold”: An Analysis of the Synthetic Complexity of Efficient Polymer Donors for Polymer Solar Cells
journal, January 2015
- Po, Riccardo; Bianchi, Gabriele; Carbonera, Chiara
- Macromolecules, Vol. 48, Issue 3
Co(ii ), Ni(ii ), Cu(ii ) and Zn(ii ) complexes of tetraphenylazadipyrromethene
journal, January 2009
- Palma, Aniello; Gallagher, John F.; Müller-Bunz, Helge
- Dalton Trans., Issue 2
Identifying the Nature of Charge Recombination in Organic Solar Cells from Charge‐Transfer State Electroluminescence
journal, May 2012
- Wetzelaer, Gert‐Jan A. H.; Kuik, Martijn; Blom, Paul W. M.
- Advanced Energy Materials, Vol. 2, Issue 10
Light intensity dependence of open-circuit voltage of polymer:fullerene solar cells
journal, March 2005
- Koster, L. J. A.; Mihailetchi, V. D.; Ramaker, R.
- Applied Physics Letters, Vol. 86, Issue 12
Boron Subphthalocyanines as Organic Electronic Materials
journal, September 2012
- Morse, Graham E.; Bender, Timothy P.
- ACS Applied Materials & Interfaces, Vol. 4, Issue 10
Solution-processed small-molecule solar cells: breaking the 10% power conversion efficiency
journal, November 2013
- Liu, Yongsheng; Chen, Chun-Chao; Hong, Ziruo
- Scientific Reports, Vol. 3, Issue 1
Organic semiconductors: A theoretical characterization of the basic parameters governing charge transport
journal, April 2002
- Bredas, J. L.; Calbert, J. P.; da Silva Filho, D. A.
- Proceedings of the National Academy of Sciences, Vol. 99, Issue 9
Nonfullerene Acceptor Molecules for Bulk Heterojunction Organic Solar Cells
journal, February 2018
- Zhang, Guangye; Zhao, Jingbo; Chow, Philip C. Y.
- Chemical Reviews, Vol. 118, Issue 7
Recent Advances in Bulk Heterojunction Polymer Solar Cells
journal, August 2015
- Lu, Luyao; Zheng, Tianyue; Wu, Qinghe
- Chemical Reviews, Vol. 115, Issue 23
Stability: next focus in organic solar cells based on non-fullerene acceptors
journal, January 2021
- Li, Yawen; Li, Tengfei; Lin, Yuze
- Materials Chemistry Frontiers, Vol. 5, Issue 7
Noncovalent Intermolecular Interactions in Organic Electronic Materials: Implications for the Molecular Packing vs Electronic Properties of Acenes
journal, November 2015
- Sutton, Christopher; Risko, Chad; Brédas, Jean-Luc
- Chemistry of Materials, Vol. 28, Issue 1
Organic field‐effect transistors with high mobility based on copper phthalocyanine
journal, November 1996
- Bao, Zhenan; Lovinger, Andrew J.; Dodabalapur, Ananth
- Applied Physics Letters, Vol. 69, Issue 20
Interlayers for non-fullerene based polymer solar cells: distinctive features and challenges
journal, January 2021
- Sorrentino, Roberto; Kozma, Erika; Luzzati, Silvia
- Energy & Environmental Science, Vol. 14, Issue 1
Highly Efficient Non-Fused-Ring Electron Acceptors Enabled by the Conformational Lock and Structural Isomerization Effects
journal, May 2021
- Zhao, Jun; Xu, Xiaopeng; Yu, Liyang
- ACS Applied Materials & Interfaces, Vol. 13, Issue 21
Fine-Tuning of Crystal Packing and Charge Transport Properties of BDOPV Derivatives through Fluorine Substitution
journal, December 2015
- Dou, Jin-Hu; Zheng, Yu-Qing; Yao, Ze-Fan
- Journal of the American Chemical Society, Vol. 137, Issue 50
Effects of Aromatic Trifluoromethylation, Fluorination, and Methylation on Intermolecular π–π Interactions
journal, July 2013
- Mottishaw, Jeffery D.; Sun, Haoran
- The Journal of Physical Chemistry A, Vol. 117, Issue 33
Exploiting Noncovalently Conformational Locking as a Design Strategy for High Performance Fused-Ring Electron Acceptor Used in Polymer Solar Cells
journal, February 2017
- Liu, Yahui; Zhang, Zhe; Feng, Shiyu
- Journal of the American Chemical Society, Vol. 139, Issue 9
Next-generation organic photovoltaics based on non-fullerene acceptors
journal, February 2018
- Cheng, Pei; Li, Gang; Zhan, Xiaowei
- Nature Photonics, Vol. 12, Issue 3
Surpassing 13% Efficiency for Polythiophene Organic Solar Cells Processed from Nonhalogenated Solvent
journal, May 2021
- Xiao, Jingyang; Jia, Xiao'e; Duan, Chunhui
- Advanced Materials, Vol. 33, Issue 25
Structure of the Lowest Temperature Phase of the Solid Benzene–Hexafluorobenzene Adduct
journal, December 1992
- Williams, Jeffrey Huw; Cockcroft, Jeremy Karl; Fitch, Andrew Nicholas
- Angewandte Chemie International Edition in English, Vol. 31, Issue 12
P-19: High Performance Porphyrin Semiconductor for Transistor Applications
journal, January 2005
- Aramaki, Shinji; Yoshiyama, Ruichi; Sakai, Masayoshi
- SID Symposium Digest of Technical Papers, Vol. 36, Issue 1
Charge carrier recombination in organic solar cells
journal, December 2013
- Proctor, Christopher M.; Kuik, Martijn; Nguyen, Thuc-Quyen
- Progress in Polymer Science, Vol. 38, Issue 12
Structure–Property Study of Homoleptic Zinc(II) Complexes of Di(arylethynyl) Azadipyrromethene as Nonfullerene Acceptors for Organic Photovoltaics: Effect of the Aryl Group
journal, March 2020
- Wang, Chunlai; Zhao, Muyuan; Rheingold, Arnold L.
- The Journal of Physical Chemistry C, Vol. 124, Issue 16
From lab to fab: how must the polymer solar cell materials design change? – an industrial perspective
journal, January 2014
- Po, Riccardo; Bernardi, Andrea; Calabrese, Anna
- Energy & Environmental Science, Vol. 7, Issue 3
Integrated Materials Design of Organic Semiconductors for Field-Effect Transistors
journal, April 2013
- Mei, Jianguo; Diao, Ying; Appleton, Anthony L.
- Journal of the American Chemical Society, Vol. 135, Issue 18