Dynamic broadening alters triplet extinction coefficients in fluorene oligomers and polymers
Abstract
We report Tn ← T1 spectra and extinction coefficients, ε, and other properties as functions of chain length for a series of fluorene oligomers, oFn, and polymers, pFn, with n = 2–84 repeat units. We find that ε increases with length, peaking at 159 400 M–1 cm–1 for oF3 and then decreases for longer chains. ε does not scale with 1/n or e–n to reach a constant value at long length, as predicted by the commonly applied oligomer extrapolation approximation, although spectral shifts, oscillator strengths, and transition dipole moments do reach limiting values for chains near 10 units long. While computations describe the triplet in oF2 and oF3 as having similar geometries with a single flattened dihedral angle between units, computations and simulations suggest that in longer oligomers motion along the chains of the short 2–3 unit, the long T1 state is probably the source of the unusual changes in ε. Furthermore, these occur because hopping along the chain is sufficiently fast that the dihedrals between fluorene units cannot fully relax. At a length near 10 units, hopping and dihedral angle changes produce a steady state distribution of geometries with only small changes from the ground state, which persist formore »
- Authors:
-
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sirindhorn International Inst. of Technology (SIIT), Bangkok (Thailand)
- Kyoto Inst. of Technology, Kyoto (Japan)
- 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:
- 1583112
- Alternate Identifier(s):
- OSTI ID: 1581666
- Report Number(s):
- BNL-213532-2020-JAAM
Journal ID: ISSN 0021-9606
- Grant/Contract Number:
- SC0012704; AC02-98-CH10886
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 152; Journal Issue: 2; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 14 SOLAR ENERGY
Citation Formats
Cook, Andrew R., Girimonti, Anthony, Sreearunothai, Paiboon, Asaoka, Sadayuki, and Miller, John R. Dynamic broadening alters triplet extinction coefficients in fluorene oligomers and polymers. United States: N. p., 2020.
Web. doi:10.1063/1.5132798.
Cook, Andrew R., Girimonti, Anthony, Sreearunothai, Paiboon, Asaoka, Sadayuki, & Miller, John R. Dynamic broadening alters triplet extinction coefficients in fluorene oligomers and polymers. United States. https://doi.org/10.1063/1.5132798
Cook, Andrew R., Girimonti, Anthony, Sreearunothai, Paiboon, Asaoka, Sadayuki, and Miller, John R. Wed .
"Dynamic broadening alters triplet extinction coefficients in fluorene oligomers and polymers". United States. https://doi.org/10.1063/1.5132798. https://www.osti.gov/servlets/purl/1583112.
@article{osti_1583112,
title = {Dynamic broadening alters triplet extinction coefficients in fluorene oligomers and polymers},
author = {Cook, Andrew R. and Girimonti, Anthony and Sreearunothai, Paiboon and Asaoka, Sadayuki and Miller, John R.},
abstractNote = {We report Tn ← T1 spectra and extinction coefficients, ε, and other properties as functions of chain length for a series of fluorene oligomers, oFn, and polymers, pFn, with n = 2–84 repeat units. We find that ε increases with length, peaking at 159 400 M–1 cm–1 for oF3 and then decreases for longer chains. ε does not scale with 1/n or e–n to reach a constant value at long length, as predicted by the commonly applied oligomer extrapolation approximation, although spectral shifts, oscillator strengths, and transition dipole moments do reach limiting values for chains near 10 units long. While computations describe the triplet in oF2 and oF3 as having similar geometries with a single flattened dihedral angle between units, computations and simulations suggest that in longer oligomers motion along the chains of the short 2–3 unit, the long T1 state is probably the source of the unusual changes in ε. Furthermore, these occur because hopping along the chain is sufficiently fast that the dihedrals between fluorene units cannot fully relax. At a length near 10 units, hopping and dihedral angle changes produce a steady state distribution of geometries with only small changes from the ground state, which persist for longer chains. Additional decreases in ε from pF28 to pF84 are plausibly due to a small number of chain defects which result in loss of triplets.},
doi = {10.1063/1.5132798},
journal = {Journal of Chemical Physics},
number = 2,
volume = 152,
place = {United States},
year = {Wed Jan 08 00:00:00 EST 2020},
month = {Wed Jan 08 00:00:00 EST 2020}
}
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