Atomic-Level Insight into the Postsynthesis Band Gap Engineering of a Lewis Base Polymer Using Lewis Acid Tris(pentafluorophenyl)borane
Abstract
Here, we investigate the binding properties of the Lewis acid tris(pentafluorophenyl)borane with a Lewis base semiconducting polymer, PFPT, and the subsequent mechanism of band gap reduction. Experiments and quantum chemical calculations confirm that the formation of a Lewis acid adduct is energetically favorable (ΔG° < -0.2 eV), with preferential binding at the pyridyl nitrogen in the polymer backbone over other Lewis base sites. Upon adduct formation, ultraviolet photoelectron spectroscopy indicates only a slight decrease in the HOMO energy, implying that a larger reduction in the LUMO energy is primarily responsible for the observed optical band gap narrowing (ΔEopt = 0.3 eV). Herein, we also provide the first spatially resolved picture of how Lewis acid adducts form in heterogeneous, disordered polymer/tris(pentafluorophenyl)borane thin films via one- (1D) and two-dimensional (2D) solid-state nuclear magnetic resonance. Notably, solid-state 1D 11B, 13C{1H}, and 13C{19F} cross-polarization magic-angle spinning (CP-MAS) NMR and 2D 1H{19F} and 1H{1H} correlation NMR analyses establish that BCF molecules are intercalated between branched C16H33 side chains with the boron atom facing toward the pyridyl nitrogen atoms of PFPT.
- Authors:
-
- Univ. of California, Santa Barbara, CA (United States)
- Univ. of California, Santa Barbara, CA (United States); Univ. of Bayreuth (Germany)
- Univ. of Bayreuth (Germany)
- Publication Date:
- Research Org.:
- Univ. of California, Santa Barbara, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Alexander von Humboldt Foundation; Bavaria California Technology Centre (BaCaTec); National Science Foundation (NSF); Mitsubishi Chemical-Centre for Advanced Materials
- OSTI Identifier:
- 1593943
- Alternate Identifier(s):
- OSTI ID: 1661629
- Grant/Contract Number:
- SC0017659; AC02-05CH11231; 1650114; DMR-1720256
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 31; Journal Issue: 17; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Adducts; Lewis acids; Nitrogen; Nuclear magnetic resonance spectroscopy; Polymers
Citation Formats
Yurash, Brett, Leifert, Dirk, Reddy, G. N. Manjunatha, Cao, David Xi, Biberger, Simon, Brus, Viktor V., Seifrid, Martin, Santiago, Peter J., Köhler, Anna, Chmelka, Bradley F., Bazan, Guillermo C., and Nguyen, Thuc-Quyen. Atomic-Level Insight into the Postsynthesis Band Gap Engineering of a Lewis Base Polymer Using Lewis Acid Tris(pentafluorophenyl)borane. United States: N. p., 2019.
Web. doi:10.1021/acs.chemmater.9b01224.
Yurash, Brett, Leifert, Dirk, Reddy, G. N. Manjunatha, Cao, David Xi, Biberger, Simon, Brus, Viktor V., Seifrid, Martin, Santiago, Peter J., Köhler, Anna, Chmelka, Bradley F., Bazan, Guillermo C., & Nguyen, Thuc-Quyen. Atomic-Level Insight into the Postsynthesis Band Gap Engineering of a Lewis Base Polymer Using Lewis Acid Tris(pentafluorophenyl)borane. United States. https://doi.org/10.1021/acs.chemmater.9b01224
Yurash, Brett, Leifert, Dirk, Reddy, G. N. Manjunatha, Cao, David Xi, Biberger, Simon, Brus, Viktor V., Seifrid, Martin, Santiago, Peter J., Köhler, Anna, Chmelka, Bradley F., Bazan, Guillermo C., and Nguyen, Thuc-Quyen. Wed .
"Atomic-Level Insight into the Postsynthesis Band Gap Engineering of a Lewis Base Polymer Using Lewis Acid Tris(pentafluorophenyl)borane". United States. https://doi.org/10.1021/acs.chemmater.9b01224. https://www.osti.gov/servlets/purl/1593943.
@article{osti_1593943,
title = {Atomic-Level Insight into the Postsynthesis Band Gap Engineering of a Lewis Base Polymer Using Lewis Acid Tris(pentafluorophenyl)borane},
author = {Yurash, Brett and Leifert, Dirk and Reddy, G. N. Manjunatha and Cao, David Xi and Biberger, Simon and Brus, Viktor V. and Seifrid, Martin and Santiago, Peter J. and Köhler, Anna and Chmelka, Bradley F. and Bazan, Guillermo C. and Nguyen, Thuc-Quyen},
abstractNote = {Here, we investigate the binding properties of the Lewis acid tris(pentafluorophenyl)borane with a Lewis base semiconducting polymer, PFPT, and the subsequent mechanism of band gap reduction. Experiments and quantum chemical calculations confirm that the formation of a Lewis acid adduct is energetically favorable (ΔG° < -0.2 eV), with preferential binding at the pyridyl nitrogen in the polymer backbone over other Lewis base sites. Upon adduct formation, ultraviolet photoelectron spectroscopy indicates only a slight decrease in the HOMO energy, implying that a larger reduction in the LUMO energy is primarily responsible for the observed optical band gap narrowing (ΔEopt = 0.3 eV). Herein, we also provide the first spatially resolved picture of how Lewis acid adducts form in heterogeneous, disordered polymer/tris(pentafluorophenyl)borane thin films via one- (1D) and two-dimensional (2D) solid-state nuclear magnetic resonance. Notably, solid-state 1D 11B, 13C{1H}, and 13C{19F} cross-polarization magic-angle spinning (CP-MAS) NMR and 2D 1H{19F} and 1H{1H} correlation NMR analyses establish that BCF molecules are intercalated between branched C16H33 side chains with the boron atom facing toward the pyridyl nitrogen atoms of PFPT.},
doi = {10.1021/acs.chemmater.9b01224},
journal = {Chemistry of Materials},
number = 17,
volume = 31,
place = {United States},
year = {Wed May 15 00:00:00 EDT 2019},
month = {Wed May 15 00:00:00 EDT 2019}
}
Web of Science
Works referenced in this record:
Introduction: Organic Electronics and Optoelectronics
journal, April 2007
- Forrest, Stephen R.; Thompson, Mark E.
- Chemical Reviews, Vol. 107, Issue 4
Conjugated Oligomers with Terminal Donor–Acceptor Substitution
journal, April 2005
- Meier, Herbert
- Angewandte Chemie International Edition, Vol. 44, Issue 17
High-mobility Ambipolar Transistors and High-gain Inverters from a Donor-Acceptor Copolymer Semiconductor
journal, January 2010
- Kim, Felix Sunjoo; Guo, Xugang; Watson, Mark D.
- Advanced Materials, Vol. 22, Issue 4, p. 478-482
Polymer-Fullerene Bulk-Heterojunction Solar Cells
journal, April 2009
- Dennler, Gilles; Scharber, Markus C.; Brabec, Christoph J.
- Advanced Materials, Vol. 21, Issue 13, p. 1323-1338
Highly efficient organic light-emitting diodes from delayed fluorescence
journal, December 2012
- Uoyama, Hiroki; Goushi, Kenichi; Shizu, Katsuyuki
- Nature, Vol. 492, Issue 7428
High-Performance Organic Light-Emitting Diodes Based on Intramolecular Charge-Transfer Emission from Donor–Acceptor Molecules: Significance of Electron- Donor Strength and Molecular Geometry
journal, May 2006
- Kulkarni, A. P.; Kong, X.; Jenekhe, S. A.
- Advanced Functional Materials, Vol. 16, Issue 8
Solution-processed small-molecule solar cells with 6.7% efficiency
journal, November 2011
- Sun, Yanming; Welch, Gregory C.; Leong, Wei Lin
- Nature Materials, Vol. 11, Issue 1, p. 44-48
Influence of the Electron Deficient Co‐Monomer on the Optoelectronic Properties and Photovoltaic Performance of Dithienogermole‐based Co‐Polymers
journal, October 2013
- Yau, Chin Pang; Fei, Zhuping; Ashraf, Raja Shahid
- Advanced Functional Materials, Vol. 24, Issue 5
Hole Mobility and Electron Injection Properties of D-A Conjugated Copolymers with Fluorinated Phenylene Acceptor Units
journal, January 2017
- Wang, Ming; Ford, Michael J.; Lill, Alexander T.
- Advanced Materials, Vol. 29, Issue 7
Band Gap Control in Conjugated Oligomers via Lewis Acids
journal, August 2009
- Welch, Gregory C.; Coffin, Robert; Peet, Jeff
- Journal of the American Chemical Society, Vol. 131, Issue 31, p. 10802-10803
Unusual Doping of Donor–Acceptor-Type Conjugated Polymers Using Lewis Acids
journal, March 2014
- Poverenov, Elena; Zamoshchik, Natalia; Patra, Asit
- Journal of the American Chemical Society, Vol. 136, Issue 13
Lewis Acid Adducts of Narrow Band Gap Conjugated Polymers
journal, March 2011
- Welch, Gregory C.; Bazan, Guillermo C.
- Journal of the American Chemical Society, Vol. 133, Issue 12
B(C 6 F 5 ) 3 : A Lewis Acid that Brings the Light to the Solid State
journal, December 2015
- Hansmann, Max M.; López-Andarias, Alicia; Rettenmeier, Eva
- Angewandte Chemie International Edition, Vol. 55, Issue 3
Acid-Responsive Absorption and Emission of 5- N -Arylaminothiazoles: Emission of White Light from a Single Fluorescent Dye and a Lewis Acid
journal, August 2016
- Yamaguchi, Kirara; Murai, Toshiaki; Guo, Jing-Dong
- ChemistryOpen, Vol. 5, Issue 5
Lewis Acid–Base Chemistry of 7-Azaisoindigo-Based Organic Semiconductors
journal, July 2017
- Randell, Nicholas M.; Fransishyn, Kyle M.; Kelly, Timothy L.
- ACS Applied Materials & Interfaces, Vol. 9, Issue 29
Color Tuning in Polymer Light-Emitting Diodes with Lewis Acids
journal, June 2012
- Zalar, Peter; Henson, Zachary B.; Welch, Gregory C.
- Angewandte Chemie, Vol. 124, Issue 30
Heteroatomic Conjugated Polymers and the Spectral Tuning of Electroluminescence via a Supramolecular Coordination Strategy
journal, September 2016
- Lin, Jinyi; Liu, Bin; Yu, Mengna
- Macromolecular Rapid Communications, Vol. 37, Issue 22
Increased Mobility Induced by Addition of a Lewis Acid to a Lewis Basic Conjugated Polymer
journal, October 2013
- Zalar, Peter; Kuik, Martijn; Henson, Zachary B.
- Advanced Materials, Vol. 26, Issue 5
p-Type Doping of Poly(3-hexylthiophene) with the Strong Lewis Acid Tris(pentafluorophenyl)borane
journal, September 2016
- Pingel, Patrick; Arvind, Malavika; Kölln, Lisa
- Advanced Electronic Materials, Vol. 2, Issue 10
Improved Performance and Reproducibility of Perovskite Solar Cells by Well-Soluble Tris(pentafluorophenyl)borane as a p-Type Dopant
journal, May 2017
- Ye, Tengling; Wang, Junhai; Chen, Wenbo
- ACS Applied Materials & Interfaces, Vol. 9, Issue 21
Lewis Acid Doping Induced Synergistic Effects on Electronic and Morphological Structure for Donor and Acceptor in Polymer Solar Cells
journal, March 2018
- Yan, Han; Chen, Jianya; Zhou, Ke
- Advanced Energy Materials, Vol. 8, Issue 19
Doping of Large Ionization Potential Indenopyrazine Polymers via Lewis Acid Complexation with Tris(pentafluorophenyl)borane: A Simple Method for Improving the Performance of Organic Thin-Film Transistors
journal, October 2016
- Han, Yang; Barnes, George; Lin, Yen-Hung
- Chemistry of Materials, Vol. 28, Issue 21
Remarkable Enhancement of the Hole Mobility in Several Organic Small-Molecules, Polymers, and Small-Molecule:Polymer Blend Transistors by Simple Admixing of the Lewis Acid p-Dopant B(C 6 F 5 ) 3
journal, October 2017
- Panidi, Julianna; Paterson, Alexandra F.; Khim, Dongyoon
- Advanced Science, Vol. 5, Issue 1
A Planar Cyclopentadithiophene–Benzothiadiazole-Based Copolymer with sp 2 -Hybridized Bis(alkylsulfanyl)methylene Substituents for Organic Thermoelectric Devices
journal, April 2018
- Lee, Jiae; Kim, Jaeyun; Nguyen, Thanh Luan
- Macromolecules, Vol. 51, Issue 9
Tris(pentafluorophenyl)borane: a special boron Lewis acid for special reactions
journal, January 2005
- Erker, Gerhard
- Dalton Transactions, Issue 11
Pentafluorophenylboranes: from obscurity to applications
journal, January 1997
- Piers, Warren E.; Chivers, Tristram
- Chemical Society Reviews, Vol. 26, Issue 5
Solution and Solid-State Characteristics of Imine Adducts with Tris(pentafluorophenyl)borane
journal, April 2002
- Blackwell, James M.; Piers, Warren E.; Parvez, Masood
- Organometallics, Vol. 21, Issue 7
Complexes of tris(pentafluorophenyl)boron with nitrogen-containing compounds: Synthesis, reactivity and metallocene activation
journal, January 2006
- Focante, Francesca; Mercandelli, Pierluigi; Sironi, Angelo
- Coordination Chemistry Reviews, Vol. 250, Issue 1-2
Synthesis and Reactivity of (C 6 F 5 ) 3 B− N -Heterocycle Complexes. 1. Generation of Highly Acidic sp 3 Carbons in Pyrroles and Indoles
journal, July 2003
- Guidotti, Simona; Camurati, Isabella; Focante, Francesca
- The Journal of Organic Chemistry, Vol. 68, Issue 14
Interplay of Structure and Dynamics in Functional Macromolecular and Supramolecular Systems As Revealed by Magnetic Resonance Spectroscopy
journal, August 2015
- Hansen, Michael Ryan; Graf, Robert; Spiess, Hans Wolfgang
- Chemical Reviews, Vol. 116, Issue 3
A Strategy for Revealing the Packing in Semicrystalline π-Conjugated Polymers: Crystal Structure of Bulk Poly-3-hexyl-thiophene (P3HT)
journal, October 2012
- Dudenko, Dmytro; Kiersnowski, Adam; Shu, Jie
- Angewandte Chemie International Edition, Vol. 51, Issue 44
Self-Assembly of Dendronized Perylene Bisimides into Complex Helical Columns
journal, August 2011
- Percec, Virgil; Peterca, Mihai; Tadjiev, Timur
- Journal of the American Chemical Society, Vol. 133, Issue 31
Direct Observation of the Relationship between Molecular Topology and Bulk Morphology for a π-Conjugated Material
journal, February 2019
- Seifrid, Martin T.; Reddy, G. N. Manjunatha; Zhou, Cheng
- Journal of the American Chemical Society, Vol. 141, Issue 13
Interplay of Noncovalent Interactions in Ribbon-like Guanosine Self-Assembly: An NMR Crystallography Study
journal, November 2015
- Reddy, G. N. Manjunatha; Marsh, Andrew; Davis, Jeffery T.
- Crystal Growth & Design, Vol. 15, Issue 12
Donor–acceptor stacking arrangements in bulk and thin-film high-mobility conjugated polymers characterized using molecular modelling and MAS and surface-enhanced solid-state NMR spectroscopy
journal, January 2017
- Chaudhari, Sachin R.; Griffin, John M.; Broch, Katharina
- Chemical Science, Vol. 8, Issue 4
Use of X-Ray Diffraction, Molecular Simulations, and Spectroscopy to Determine the Molecular Packing in a Polymer-Fullerene Bimolecular Crystal
journal, September 2012
- Miller, Nichole Cates; Cho, Eunkyung; Junk, Matthias J. N.
- Advanced Materials, Vol. 24, Issue 45
Sub-ns triplet state formation by non-geminate recombination in PSBTBT:PC 70 BM and PCPDTBT:PC 60 BM organic solar cells
journal, January 2015
- Etzold, Fabian; Howard, Ian A.; Forler, Nina
- Energy & Environmental Science, Vol. 8, Issue 5
1 H and 19 F NMR Investigation of the Reaction of B(C 6 F 5 ) 3 with Water in Toluene Solution
journal, November 2001
- Beringhelli, Tiziana; Maggioni, Daniela; D'Alfonso, Giuseppe
- Organometallics, Vol. 20, Issue 23
Trap-Limited Exciton Diffusion in Organic Semiconductors
journal, December 2013
- Mikhnenko, Oleksandr V.; Kuik, Martijn; Lin, Jason
- Advanced Materials, Vol. 26, Issue 12
Determining the Crystal Structures of Peptide Analogs of Boronic Acid in the Absence of Single Crystals: Intricate Motifs of Ixazomib Citrate Revealed by XRPD Guided by ss-NMR
journal, April 2018
- Hušák, Michal; Jegorov, Alexandr; Rohlíček, Jan
- Crystal Growth & Design, Vol. 18, Issue 6
G4-Quartet·M + Borate Hydrogels
journal, April 2015
- Peters, Gretchen Marie; Skala, Luke P.; Plank, Taylor N.
- Journal of the American Chemical Society, Vol. 137, Issue 17
Doping-Induced Carrier Density Modulation in Polymer Field-Effect Transistors
journal, November 2015
- Lee, Byoung Hoon; Bazan, Guillermo C.; Heeger, Alan J.
- Advanced Materials, Vol. 28, Issue 1
Improvement of Interfacial Contacts for New Small-Molecule Bulk-Heterojunction Organic Photovoltaics
journal, August 2012
- Garcia, Andres; Welch, Gregory C.; Ratcliff, Erin L.
- Advanced Materials, Vol. 24, Issue 39
Co-existence of Distinct Supramolecular Assemblies in Solution and in the Solid State
journal, December 2016
- Reddy, G. N. Manjunatha; Huqi, Aida; Iuga, Dinu
- Chemistry - A European Journal, Vol. 23, Issue 10
Macroscopic Structural Compositions of π-Conjugated Polymers: Combined Insights from Solid-State NMR and Molecular Dynamics Simulations
journal, August 2017
- Melnyk, Anton; Junk, Matthias J. N.; McGehee, Michael D.
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 17
Every Atom Counts: Elucidating the Fundamental Impact of Structural Change in Conjugated Polymers for Organic Photovoltaics
journal, April 2018
- Lo, Chi Kin; Gautam, Bhoj R.; Selter, Philipp
- Chemistry of Materials, Vol. 30, Issue 9
Molecular Interactions and Ordering in Electrically Doped Polymers: Blends of PBTTT and F 4 TCNQ
journal, September 2014
- Cochran, Justin E.; Junk, Matthias J. N.; Glaudell, A. M.
- Macromolecules, Vol. 47, Issue 19
N–H⋯F hydrogen bonds in fluorinated benzanilides: NMR and DFT study
journal, January 2010
- Manjunatha Reddy, G. N.; Vasantha Kumar, M. V.; Guru Row, T. N.
- Physical Chemistry Chemical Physics, Vol. 12, Issue 40
The exciton binding energy in luminescent conjugated polymers
journal, May 1996
- Brédas, Jean-Luc; Cornil, Jérôme; Heeger, Alan J.
- Advanced Materials, Vol. 8, Issue 5
Exciton binding energies in organic semiconductors
journal, October 2003
- Knupfer, M.
- Applied Physics A, Vol. 77, Issue 5
Harvesting the Full Potential of Photons with Organic Solar Cells
journal, December 2015
- Ran, Niva A.; Love, John A.; Takacs, Christopher J.
- Advanced Materials, Vol. 28, Issue 7
25th Anniversary Article: Recent Advances in n-Type and Ambipolar Organic Field-Effect Transistors
journal, August 2013
- Zhao, Yan; Guo, Yunlong; Liu, Yunqi
- Advanced Materials, Vol. 25, Issue 38
Electron and Ambipolar Transport in Organic Field-Effect Transistors
journal, April 2007
- Zaumseil, Jana; Sirringhaus, Henning
- Chemical Reviews, Vol. 107, Issue 4, p. 1296-1323
Efficient light-emitting diodes based on polymers with high electron affinities
journal, October 1993
- Greenham, N. C.; Moratti, S. C.; Bradley, D. D. C.
- Nature, Vol. 365, Issue 6447
Efficient electron injection in blue-emitting polymer light-emitting diodes with LiF/Ca/Al cathodes
journal, July 2001
- Brown, T. M.; Friend, R. H.; Millard, I. S.
- Applied Physics Letters, Vol. 79, Issue 2
Offset energies at organic semiconductor heterojunctions and their influence on the open-circuit voltage of thin-film solar cells
journal, March 2007
- Rand, Barry P.; Burk, Diana P.; Forrest, Stephen R.
- Physical Review B, Vol. 75, Issue 11
Regioregular Pyridal[2,1,3]thiadiazole π-Conjugated Copolymers
journal, November 2011
- Ying, Lei; Hsu, Ben B. Y.; Zhan, Hongmei
- Journal of the American Chemical Society, Vol. 133, Issue 46
Measurement of absolute photoluminescence quantum efficiencies in conjugated polymers
journal, July 1995
- Greenham, N. C.; Samuel, I. D. W.; Hayes, G. R.
- Chemical Physics Letters, Vol. 241, Issue 1-2
Design of heteronuclear decoupling sequences for solids
journal, February 2000
- Khitrin, Anatoly; Fung, B. M.
- The Journal of Chemical Physics, Vol. 112, Issue 5
Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993
- Becke, Axel D.
- The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections
journal, January 2008
- Chai, Jeng-Da; Head-Gordon, Martin
- Physical Chemistry Chemical Physics, Vol. 10, Issue 44
Excitation Gaps of Finite-Sized Systems from Optimally Tuned Range-Separated Hybrid Functionals
journal, April 2012
- Kronik, Leeor; Stein, Tamar; Refaely-Abramson, Sivan
- Journal of Chemical Theory and Computation, Vol. 8, Issue 5