Small Changes With Big Consequences: Swapping Two Atoms In Side Chains Changes Phenylene‐Ethynylene Packing And Fluorescence
Abstract
Abstract Engineering the properties of conjugated materials in the solid state is an unsolved, ongoing challenge important to fundamental understanding of how non‐covalent interactions dictate packing and key properties, as well as the development of technologies based in organic optoelectronics. The most common design paradigm of such materials divide them into a “main chain” with extended conjugation, the chemical structure of which determines optoelectronic properties, and “side chains” not conjugated to the backbone, which provide solubility when they are long alkyl chains. This paper describes comparisons between phenylene‐ethynylene molecules in which slight changes to the structure of “side chains”—swapping hydrogen and fluorine atomic position on an aromatic ring—results in unexpectedly large changes in the solid‐state optical properties. In a pair of anisyl‐terminated three‐ring phenylene‐ethynylenes, switching the side chain arenes of benzyl esters from 2,4,6‐trifluoro to 2,3,6‐trifluoro results in a shift in fluorescence emission spectra of over 100 nm, as well as the opposite direction of force‐induced shifting of emission. Through a combination X‐ray crystal structures, electronic structure calculations, and comparisons with other derivatives, we describe how the 2,4,6‐trifluorinated side chains yield cofacial fluoroarene‐arene stacking interactions that twist the PE backbone out of conjugation, while the 2,3,6‐trifluoro side chains do notmore »
- Authors:
-
- Department of Chemistry Tufts University 62 Talbot Avenue Medford MA 02155 USA
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1479157
- Grant/Contract Number:
- SC0016423
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Chemistry - A European Journal
- Additional Journal Information:
- Journal Name: Chemistry - A European Journal Journal Volume: 24 Journal Issue: 64; Journal ID: ISSN 0947-6539
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Sharber, Seth A., and Thomas, III, Samuel W. Small Changes With Big Consequences: Swapping Two Atoms In Side Chains Changes Phenylene‐Ethynylene Packing And Fluorescence. Germany: N. p., 2018.
Web. doi:10.1002/chem.201804648.
Sharber, Seth A., & Thomas, III, Samuel W. Small Changes With Big Consequences: Swapping Two Atoms In Side Chains Changes Phenylene‐Ethynylene Packing And Fluorescence. Germany. https://doi.org/10.1002/chem.201804648
Sharber, Seth A., and Thomas, III, Samuel W. Fri .
"Small Changes With Big Consequences: Swapping Two Atoms In Side Chains Changes Phenylene‐Ethynylene Packing And Fluorescence". Germany. https://doi.org/10.1002/chem.201804648.
@article{osti_1479157,
title = {Small Changes With Big Consequences: Swapping Two Atoms In Side Chains Changes Phenylene‐Ethynylene Packing And Fluorescence},
author = {Sharber, Seth A. and Thomas, III, Samuel W.},
abstractNote = {Abstract Engineering the properties of conjugated materials in the solid state is an unsolved, ongoing challenge important to fundamental understanding of how non‐covalent interactions dictate packing and key properties, as well as the development of technologies based in organic optoelectronics. The most common design paradigm of such materials divide them into a “main chain” with extended conjugation, the chemical structure of which determines optoelectronic properties, and “side chains” not conjugated to the backbone, which provide solubility when they are long alkyl chains. This paper describes comparisons between phenylene‐ethynylene molecules in which slight changes to the structure of “side chains”—swapping hydrogen and fluorine atomic position on an aromatic ring—results in unexpectedly large changes in the solid‐state optical properties. In a pair of anisyl‐terminated three‐ring phenylene‐ethynylenes, switching the side chain arenes of benzyl esters from 2,4,6‐trifluoro to 2,3,6‐trifluoro results in a shift in fluorescence emission spectra of over 100 nm, as well as the opposite direction of force‐induced shifting of emission. Through a combination X‐ray crystal structures, electronic structure calculations, and comparisons with other derivatives, we describe how the 2,4,6‐trifluorinated side chains yield cofacial fluoroarene‐arene stacking interactions that twist the PE backbone out of conjugation, while the 2,3,6‐trifluoro side chains do not stack, instead yielding more coplanar PE backbones that form intermolecular aggregates. Overall, this work demonstrates how slight modifications to parts of conjugated materials normally considered ancillary to optoelectronic properties can determine their solid‐state properties, epitomizing the challenge of rational design but at the same time offering opportunities for materials discovery and improved understanding of non‐covalent interactions.},
doi = {10.1002/chem.201804648},
journal = {Chemistry - A European Journal},
number = 64,
volume = 24,
place = {Germany},
year = {Fri Oct 26 00:00:00 EDT 2018},
month = {Fri Oct 26 00:00:00 EDT 2018}
}
https://doi.org/10.1002/chem.201804648
Web of Science
Works referenced in this record:
Reversible mechanofluorochromism of aniline-terminated phenylene ethynylenes
journal, January 2018
- Sharber, Seth A.; Shih, Kuo-Chih; Mann, Arielle
- Chemical Science, Vol. 9, Issue 24
Substituent Effects That Control Conjugated Oligomer Conformation through Non-covalent Interactions
journal, March 2017
- Sharber, Seth A.; Baral, Rom Nath; Frausto, Fanny
- Journal of the American Chemical Society, Vol. 139, Issue 14
Side Chain Engineering in Solution-Processable Conjugated Polymers
journal, September 2013
- Mei, Jianguo; Bao, Zhenan
- Chemistry of Materials, Vol. 26, Issue 1
Excited-State Dynamics of Oligo( p -phenyleneethynylene): Quadratic Coupling and Torsional Motions
journal, July 2001
- Sluch, Mikhail I.; Godt, Adelheid; Bunz, Uwe H. F.
- Journal of the American Chemical Society, Vol. 123, Issue 26
Influence of halogen atoms on the structures and photophysical properties of 9,10-distyrylanthracene (DSA)
journal, January 2015
- Wu, Dong-En; Wang, Man-Ning; Luo, Yang-Hui
- CrystEngComm, Vol. 17, Issue 47
Polymorphism and mechanochromic luminescence of a highly solid-emissive quinoline-β-ketone boron difluoride dye
journal, January 2015
- Tan, Ronghua; Lin, Qifei; Wen, Ying
- CrystEngComm, Vol. 17, Issue 35
Twisting and piezochromism of phenylene-ethynylenes with aromatic interactions between side chains and main chains
journal, January 2014
- Pawle, R. H.; Haas, T. E.; Müller, P.
- Chem. Sci., Vol. 5, Issue 11
Mechanoresponsive Luminescent Molecular Assemblies: An Emerging Class of Materials
journal, October 2015
- Sagara, Yoshimitsu; Yamane, Shogo; Mitani, Masato
- Advanced Materials, Vol. 28, Issue 6
Fluorine-induced J-aggregation enhances emissive properties of a new NLO push–pull chromophore
journal, January 2014
- Botta, Chiara; Cariati, Elena; Cavallo, Gabriella
- Journal of Materials Chemistry C, Vol. 2, Issue 27
Building Blocks for n-Type Organic Electronics: Regiochemically Modulated Inversion of Majority Carrier Sign in Perfluoroarene-Modified Polythiophene Semiconductors
journal, August 2003
- Facchetti, Antonio; Yoon, Myung-Han; Stern, Charlotte L.
- Angewandte Chemie International Edition, Vol. 42, Issue 33
Halogen bonding in polymer science: from crystal engineering to functional supramolecular polymers and materials
journal, January 2015
- Berger, Gilles; Soubhye, Jalal; Meyer, Franck
- Polymer Chemistry, Vol. 6, Issue 19
H-Bonding Control of Supramolecular Ordering of Diketopyrrolopyrroles
journal, March 2017
- Fu, Chaoying; Beldon, Patrick J.; Perepichka, Dmitrii F.
- Chemistry of Materials, Vol. 29, 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
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
Remarkable Turn-On and Color-Tuned Piezochromic Luminescence: Mechanically Switching Intramolecular Charge Transfer in Molecular Crystals
journal, May 2015
- Qi, Qingkai; Qian, Jingyu; Tan, Xiao
- Advanced Functional Materials, Vol. 25, Issue 26
Interplay of Intramolecular Noncovalent Coulomb Interactions for Semicrystalline Photovoltaic Polymers
journal, August 2015
- Uddin, Mohammad Afsar; Lee, Tack Ho; Xu, Shuhao
- Chemistry of Materials, Vol. 27, Issue 17
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
Oligo(p-phenylene-ethynylene)s with Backbone Conformation Controlled by Competitive Intramolecular Hydrogen Bonds
journal, May 2011
- Hu, Wei; Yan, Qifan; Zhao, Dahui
- Chemistry - A European Journal, Vol. 17, Issue 25
Multi-color photoluminescence induced by electron-density distribution of fluorinated bistolane derivatives
journal, October 2017
- Yamada, Shigeyuki; Morita, Masato; Konno, Tsutomu
- Journal of Fluorine Chemistry, Vol. 202
Stimuli-responsive side chains for new function from conjugated materials
journal, May 2016
- Thomas, Samuel W.; Pawle, Robert H.; Smith, Zachary C.
- Journal of Photochemistry and Photobiology A: Chemistry, Vol. 322-323
Improved Solid-State Photomechanical Materials by Fluorine Substitution of 9-Anthracene Carboxylic Acid
journal, October 2014
- Zhu, Lingyan; Tong, Fei; Salinas, Christopher
- Chemistry of Materials, Vol. 26, Issue 20
Straight chain D–A copolymers based on thienothiophene and benzothiadiazole for efficient polymer field effect transistors and photovoltaic cells
journal, January 2016
- Li, Yuxiang; Lee, Tack Ho; Park, Song Yi
- Polymer Chemistry, Vol. 7, Issue 28
Bandgap Engineering of Conjugated Materials with Nonconjugated Side Chains
journal, March 2014
- Pawle, Robert H.; Agarwal, Ankita; Malveira, Stephanie
- Macromolecules, Vol. 47, Issue 7
Design strategies for organic semiconductors beyond the molecular formula
journal, August 2012
- Henson, Zachary B.; Müllen, Klaus; Bazan, Guillermo C.
- Nature Chemistry, Vol. 4, Issue 9
Incorporation of Fluorine onto Different Positions of Phenyl Substituted Benzo[1,2- b :4,5- b ′]dithiophene Unit: Influence on Photovoltaic Properties
journal, June 2015
- Yuan, Jun; Zou, Yingping; Cui, Ruili
- Macromolecules, Vol. 48, Issue 13
Building Blocks for n-Type Organic Electronics: Regiochemically Modulated Inversion of Majority Carrier Sign in Perfluoroarene-Modified Polythiophene Semiconductors
journal, August 2003
- Facchetti, Antonio; Yoon, Myung-Han; Stern, Charlotte L.
- Angewandte Chemie, Vol. 115, Issue 33
Azo⋯phenyl stacking: a persistent self-assembly motif guides the assembly of fluorinated cis-azobenzenes into photo-mechanical needle crystals
journal, January 2016
- Bushuyev, Oleksandr S.; Tomberg, Anna; Vinden, Joanna R.
- Chemical Communications, Vol. 52, Issue 10
Increased Alignment of Electronic Polymers in Liquid Crystals via Hydrogen Bonding Extension
journal, November 2006
- Hoogboom, Johan; Swager, Timothy M.
- Journal of the American Chemical Society, Vol. 128, Issue 47
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