Chain Length Dependence of Energies of Electron and Triplet Polarons in Oligofluorenes

Chen, Hung Cheng; Sreearunothai, Paiboon; Cook, Andrew R.; Asaoka, Sadayuki; Wu, Qin; Miller, John R.

doi:10.1021/acs.jpcc.7b00099

Chain Length Dependence of Energies of Electron and Triplet Polarons in Oligofluorenes

Journal Article · Wed Mar 01 00:00:00 EST 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.7b00099· OSTI ID:1349560

Chen, Hung Cheng ^[1]; Sreearunothai, Paiboon ^[2]; Cook, Andrew R. ^[1]; Asaoka, Sadayuki ^[3]; ^[4]; ^[1]

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

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.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-98CH10886

OSTI ID:: 1349560

Report Number(s):: BNL--113668-2017-JA; KC0304030

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 11 Vol. 121; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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