Chain Length Dependence of Energies of Electron and Triplet Polarons in Oligofluorenes
Abstract
Bimolecular equilibria measured the one-electron reduction potentials and triplet free energies (ΔG°T) of oligo(9,9-dihexyl)fluorenes and a polymer with lengths of n = 1–10 and 57 repeat units. We can accurately measure one-electron potentials electrochemically only for the shorter oligomers. Starting at n = 1 the free energies change rapidly with increasing length and become constant for lengths longer than the delocalization length. Both the reduction potentials and triplet energies can be understood as the sum of a free energy for a fixed polaron and a positional entropy. Furthermore, the positional entropy increases gradually with length beyond the delocalization length due to the possible occupation sites of the charge or the triplet exciton. Our results reinforce the view that charges and triplet excitons in conjugated chains exist as polarons and find that positional entropy can replace a popular empirical model of the energetics.
- Authors:
-
- Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.
- Thammasat Univ., Pathum Thani (Thailand). Sirindhorn International Inst. of Technology
- Kyoto Inst. of Technology, Sakyo-ku (Japan). Faculty of Materials Science and Engineering
- Brookhaven National Lab. (BNL), Upton, NY (United States). Center of Functional Nanomaterials
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1349560
- Report Number(s):
- BNL-113668-2017-JA
Journal ID: ISSN 1932-7447; R&D Project: CO004; KC0304030
- Grant/Contract Number:
- SC00112704; AC02-98-CH10886
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 121; Journal Issue: 11; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Chen, Hung Cheng, Sreearunothai, Paiboon, Cook, Andrew R., Asaoka, Sadayuki, Wu, Qin, and Miller, John R. Chain Length Dependence of Energies of Electron and Triplet Polarons in Oligofluorenes. United States: N. p., 2017.
Web. doi:10.1021/acs.jpcc.7b00099.
Chen, Hung Cheng, Sreearunothai, Paiboon, Cook, Andrew R., Asaoka, Sadayuki, Wu, Qin, & Miller, John R. Chain Length Dependence of Energies of Electron and Triplet Polarons in Oligofluorenes. United States. https://doi.org/10.1021/acs.jpcc.7b00099
Chen, Hung Cheng, Sreearunothai, Paiboon, Cook, Andrew R., Asaoka, Sadayuki, Wu, Qin, and Miller, John R. Wed .
"Chain Length Dependence of Energies of Electron and Triplet Polarons in Oligofluorenes". United States. https://doi.org/10.1021/acs.jpcc.7b00099. https://www.osti.gov/servlets/purl/1349560.
@article{osti_1349560,
title = {Chain Length Dependence of Energies of Electron and Triplet Polarons in Oligofluorenes},
author = {Chen, Hung Cheng and Sreearunothai, Paiboon and Cook, Andrew R. and Asaoka, Sadayuki and Wu, Qin and Miller, John R.},
abstractNote = {Bimolecular equilibria measured the one-electron reduction potentials and triplet free energies (ΔG°T) of oligo(9,9-dihexyl)fluorenes and a polymer with lengths of n = 1–10 and 57 repeat units. We can accurately measure one-electron potentials electrochemically only for the shorter oligomers. Starting at n = 1 the free energies change rapidly with increasing length and become constant for lengths longer than the delocalization length. Both the reduction potentials and triplet energies can be understood as the sum of a free energy for a fixed polaron and a positional entropy. Furthermore, the positional entropy increases gradually with length beyond the delocalization length due to the possible occupation sites of the charge or the triplet exciton. Our results reinforce the view that charges and triplet excitons in conjugated chains exist as polarons and find that positional entropy can replace a popular empirical model of the energetics.},
doi = {10.1021/acs.jpcc.7b00099},
journal = {Journal of Physical Chemistry. C},
number = 11,
volume = 121,
place = {United States},
year = {Wed Mar 01 00:00:00 EST 2017},
month = {Wed Mar 01 00:00:00 EST 2017}
}
Web of Science
Works referenced in this record:
Single Molecule Electronic Devices
journal, February 2011
- Song, Hyunwook; Reed, Mark A.; Lee, Takhee
- Advanced Materials, Vol. 23, Issue 14
Volumen und Hydratationswärme der Ionen
journal, February 1920
- Born, M.
- Zeitschrift für Physik, Vol. 1, Issue 1
Electron Transport Materials for Organic Light-Emitting Diodes
journal, November 2004
- Kulkarni, Abhishek P.; Tonzola, Christopher J.; Babel, Amit
- Chemistry of Materials, Vol. 16, Issue 23
Conjugated Polymer-Based Organic Solar Cells
journal, April 2007
- Günes, Serap; Neugebauer, Helmut; Sariciftci, Niyazi Serdar
- Chemical Reviews, Vol. 107, Issue 4, p. 1324-1338
Chain-length dependence of electronic and electrochemical properties of conjugated systems: polyacetylene, polyphenylene, polythiophene, and polypyrrole
journal, October 1983
- Bredas, J. L.; Silbey, R.; Boudreaux, D. S.
- Journal of the American Chemical Society, Vol. 105, Issue 22
Charge-Transfer and Energy-Transfer Processes in π-Conjugated Oligomers and Polymers: A Molecular Picture
journal, November 2004
- Brédas, Jean-Luc; Beljonne, David; Coropceanu, Veaceslav
- Chemical Reviews, Vol. 104, Issue 11
Chain-Length Dependence of the Electrochemical Properties of Conjugated Oligofluorenes
journal, October 2005
- Chi, Chunyan; Wegner, Gerhard
- Macromolecular Rapid Communications, Vol. 26, Issue 19
Chain-length dependence of electrochemical and electronic properties of neutral and oxidized soluble .alpha.,.alpha.-coupled thiophene oligomers
journal, September 1992
- Guay, J.; Kasai, P.; Diaz, A.
- Chemistry of Materials, Vol. 4, Issue 5
Polarons, Bipolarons, and Side-By-Side Polarons in Reduction of Oligofluorenes
journal, June 2012
- Zaikowski, Lori; Kaur, Parmeet; Gelfond, Claudia
- Journal of the American Chemical Society, Vol. 134, Issue 26
Nature and Energies of Electrons and Holes in a Conjugated Polymer, Polyfluorene
journal, December 2006
- Takeda, Norihiko; Asaoka, Sadayuki; Miller, John R.
- Journal of the American Chemical Society, Vol. 128, Issue 50
Poly(3-decylthiophene) Radical Anions and Cations in Solution: Single and Multiple Polarons and Their Delocalization Lengths in Conjugated Polymers
journal, December 2012
- Takeda, Norihiko; Miller, John R.
- The Journal of Physical Chemistry B, Vol. 116, Issue 50
Effect of Chain Extension on the Electrochemical and Electronic Properties of π-Conjugated Soluble Thienylenevinylene Oligomers
journal, November 1997
- Elandaloussi, El Hadj; Frère, Pierre; Richomme, Pascal
- Journal of the American Chemical Society, Vol. 119, Issue 44
Triplet Energies of -Conjugated Polymers
journal, February 2001
- Monkman, A. P.; Burrows, H. D.; Hartwell, L. J.
- Physical Review Letters, Vol. 86, Issue 7
Triplet state spectroscopy of conjugated polymers studied by pulse radiolysis
journal, January 2001
- Monkman, A. P.; Burrows, H. D.; Miguel, M. da G.
- Synthetic Metals, Vol. 116, Issue 1-3
Chain-Length Dependence of Singlet and Triplet Exciton Formation Rates in Organic Light-Emitting Diodes
journal, July 2004
- Beljonne, D.; Ye, A.; Shuai, Z.
- Advanced Functional Materials, Vol. 14, Issue 7
The Singlet–Triplet Exchange Energy in Conjugated Polymers
journal, January 2004
- Köhler, A.; Beljonne, D.
- Advanced Functional Materials, Vol. 14, Issue 1
Lifetime determination of fluorescence and phosphorescence of a series of oligofluorenes
journal, January 2006
- Chi, Chunyan; Im, Chan; Wegner, Gerhard
- The Journal of Chemical Physics, Vol. 124, Issue 2
Influence of Chain Length and Derivatization on the Lowest Singlet and Triplet States and Intersystem Crossing in Oligothiophenes
journal, January 1996
- Beljonne, D.; Cornil, J.; Friend, R. H.
- Journal of the American Chemical Society, Vol. 118, Issue 27
Effective conjugation length of π-conjugated systems
journal, September 2004
- Rissler, Jörg
- Chemical Physics Letters, Vol. 395, Issue 1-3
Entropy of Charge Separation in Organic Photovoltaic Cells: The Benefit of Higher Dimensionality
journal, November 2011
- Gregg, Brian A.
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 24, p. 3013-3015
Charge Photogeneration in Organic Solar Cells
journal, November 2010
- Clarke, Tracey M.; Durrant, James R.
- Chemical Reviews, Vol. 110, Issue 11, p. 6736-6767
Entropy and Disorder Enable Charge Separation in Organic Solar Cells
journal, October 2016
- Hood, Samantha N.; Kassal, Ivan
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 22
Length and Time-Dependent Rates in Diffusion-Controlled Reactions with Conjugated Polymers
journal, March 2009
- Sreearunothai, Paiboon; Asaoka, Sadayuki; Cook, Andrew R.
- The Journal of Physical Chemistry A, Vol. 113, Issue 12
The LEAF picosecond pulse radiolysis facility at Brookhaven National Laboratory
journal, November 2004
- Wishart, James F.; Cook, Andrew R.; Miller, John R.
- Review of Scientific Instruments, Vol. 75, Issue 11
Electron and organic radical anion solvation. Pulse radiolysis of tetrahydrofuran and its solutions of N-methylacetamide or pyrrolidone
journal, March 1983
- Tran-Thi, T. H.; Koulkes-Pujo, A. M.
- The Journal of Physical Chemistry, Vol. 87, Issue 7
New methods for the accurate determination of extinction and diffusion coefficients of aromatic and heteroaromatic radical anions in N,N-dimethylformamide
journal, August 1998
- Pedersen, Steen U.; Bo Christensen, Torben; Thomasen, Tove
- Journal of Electroanalytical Chemistry, Vol. 454, Issue 1-2
Triplet–Triplet Absorption Spectra of Organic Molecules in Condensed Phases
journal, January 1986
- Carmichael, Ian; Hug, Gordon L.
- Journal of Physical and Chemical Reference Data, Vol. 15, Issue 1
Extinction Coefficients of Triplet–Triplet Absorption Spectra of Organic Molecules in Condensed Phases: A Least‐Squares Analysis
journal, April 1987
- Carmichael, Ian; Helman, W. P.; Hug, G. L.
- Journal of Physical and Chemical Reference Data, Vol. 16, Issue 2
Triplet Transport to and Trapping by Acceptor End Groups on Conjugated Polyfluorene Chains
journal, September 2011
- Sreearunothai, Paiboon; Estrada, Alexis; Asaoka, Sadayuki
- The Journal of Physical Chemistry C, Vol. 115, Issue 40
Trans-stilbene phosphorescence
journal, March 1980
- Saltiel, Jack; Khalil, Gamal-Eddin; Schanze, Kirk
- Chemical Physics Letters, Vol. 70, Issue 2
Nonvertical deactivation and the lifetime and geometry of stilbene triplets in solution
journal, August 1974
- Saltiel, Jack; Thomas, Babu
- Journal of the American Chemical Society, Vol. 96, Issue 17
Multiple reversible electrochemical reduction of aromatic hydrocarbons in liquid alkylamines
journal, March 1989
- Meerholz, Klaus; Heinze, Juergen
- Journal of the American Chemical Society, Vol. 111, Issue 6
Solvation of anion radicals: gas-phase versus solution
journal, March 1989
- Shalev, Haim; Evans, Dennis H.
- Journal of the American Chemical Society, Vol. 111, Issue 7
Triplet-triplet extinction coefficients via energy transfer
journal, January 1971
- Bensasson, R.; Land, E. J.
- Transactions of the Faraday Society, Vol. 67
Triplet-triplet spectra and triplet quantum yields of some aromatic hydrocarbons in liquid solution
journal, September 1969
- Heinzelmann, W.; Labhart, H.
- Chemical Physics Letters, Vol. 4, Issue 1
Conformational changes involved in the singlet-triplet transitions of biphenyl
journal, June 1967
- Wagner, Peter John.
- Journal of the American Chemical Society, Vol. 89, Issue 12
Determination of triplet quantum yields by laser flash absorption spectroscopy
journal, July 1975
- Amand, B.; Bensasson, R.
- Chemical Physics Letters, Vol. 34, Issue 1
Radiationless conversion from the triplet state
journal, June 1962
- Hoffman, M. Z.; Porter, George
- Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, Vol. 268, Issue 1332, p. 46-56
Energy transfer in the course of triplet state quenching of aromatic hydrocarbons by nitroxyl radicals
journal, February 1978
- Kuzmin, V. A.; Tatikolov, A. S.
- Chemical Physics Letters, Vol. 53, Issue 3
Thermodynamic energies of donor and acceptor triplet states
journal, January 2008
- Merkel, Paul B.; Dinnocenzo, Joseph P.
- Journal of Photochemistry and Photobiology A: Chemistry, Vol. 193, Issue 2-3
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
journal, May 2009
- Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
- The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396
Fundamental Electrochemical Studies of Polyacetylene
journal, December 1984
- Kaufman, J. H.; Chung, T. ‐C.; Heeger, A. J.
- Journal of The Electrochemical Society, Vol. 131, Issue 12
Chemical Redox Agents for Organometallic Chemistry
journal, January 1996
- Connelly, Neil G.; Geiger, William E.
- Chemical Reviews, Vol. 96, Issue 2
Electrochemistry of nickel(II) porphyrins and chlorins
journal, March 1984
- Chang, D.; Malinski, T.; Ulman, A.
- Inorganic Chemistry, Vol. 23, Issue 7
Solvation Thermodynamics of Organic Molecules by the Molecular Integral Equation Theory: Approaching Chemical Accuracy
journal, June 2015
- Ratkova, Ekaterina L.; Palmer, David S.; Fedorov, Maxim V.
- Chemical Reviews, Vol. 115, Issue 13
Polyfluorene Derivatives: Effective Conjugation Lengths from Well-Defined Oligomers
journal, March 1998
- Klaerner, G.; Miller, R. D.
- Macromolecules, Vol. 31, Issue 6
Chain length dependence of singlet and triplet excited states of oligofluorenes: A density functional study
journal, July 2007
- Jansson, Emil; Jha, Prakash Chandra; Ågren, Hans
- Chemical Physics, Vol. 336, Issue 2-3
Comparison of the chain length dependence of the singlet- and triplet-excited states of oligofluorenes
journal, August 2005
- Wasserberg, Dorothee; Dudek, Stephen P.; Meskers, Stefan C. J.
- Chemical Physics Letters, Vol. 411, Issue 1-3
Works referencing / citing this record:
Dynamic broadening alters triplet extinction coefficients in fluorene oligomers and polymers
journal, January 2020
- Cook, Andrew R.; Girimonti, Anthony; Sreearunothai, Paiboon
- The Journal of Chemical Physics, Vol. 152, Issue 2