Abstract
Two terrylene chromophores, 2,5,10,13-tetra(tert-butyl)terrylene (1) and 2,5-di(tert-butyl)terrylene (2), were synthesized and studied to determine their singlet exciton fission (SF) efficiencies. Compound 1 crystallizes in one-dimensional stacks, whereas 2 packs in a slip-stacked, herringbone pattern of dimers motif. Strongly quenched fluorescence and rapid singlet exciton decay dynamics are observed in vapor-deposited thin films of 1 and 2. Phosphorescence measurements on thin films of 1 and 2 show that SF is only 70 meV endoergic for these chromophores. Femtosecond transient absorption experiments using low laser fluences on these films reveal rapid triplet exciton formation for both 1 (τ = 120 ± 10 ps) and 2 (τ = 320 ± 20 ps) that depends strongly on film crystallinity. The transient absorption data are consistent with formation of an excimer state prior to SF. Triplet exciton yield measurements indicate nearly quantitative SF in thin films of both chromophores in highly crystalline solvent-vapor-annealed films: 170 ± 20% for 1 and 200 ± 30% for 2. These results show that significantly different crystal morphologies of the same chromophore can both result in high-efficiency SF provided that the energetics are favorable.
| Original language | English |
|---|---|
| Pages (from-to) | 4151-4161 |
| Number of pages | 11 |
| Journal | Journal of Physical Chemistry A |
| Volume | 119 |
| Issue number | 18 |
| DOIs | |
| Publication status | Published - May 7 2015 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
Cite this
Singlet exciton fission in thin films of tert -butyl-substituted terrylenes. / Eaton, Samuel W.; Miller, Stephen A.; Margulies, Eric A.; Shoer, Leah E.; Schaller, Richard D; Wasielewski, Michael R.
In: Journal of Physical Chemistry A, Vol. 119, No. 18, 07.05.2015, p. 4151-4161.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Singlet exciton fission in thin films of tert -butyl-substituted terrylenes
AU - Eaton, Samuel W.
AU - Miller, Stephen A.
AU - Margulies, Eric A.
AU - Shoer, Leah E.
AU - Schaller, Richard D
AU - Wasielewski, Michael R
PY - 2015/5/7
Y1 - 2015/5/7
N2 - Two terrylene chromophores, 2,5,10,13-tetra(tert-butyl)terrylene (1) and 2,5-di(tert-butyl)terrylene (2), were synthesized and studied to determine their singlet exciton fission (SF) efficiencies. Compound 1 crystallizes in one-dimensional stacks, whereas 2 packs in a slip-stacked, herringbone pattern of dimers motif. Strongly quenched fluorescence and rapid singlet exciton decay dynamics are observed in vapor-deposited thin films of 1 and 2. Phosphorescence measurements on thin films of 1 and 2 show that SF is only 70 meV endoergic for these chromophores. Femtosecond transient absorption experiments using low laser fluences on these films reveal rapid triplet exciton formation for both 1 (τ = 120 ± 10 ps) and 2 (τ = 320 ± 20 ps) that depends strongly on film crystallinity. The transient absorption data are consistent with formation of an excimer state prior to SF. Triplet exciton yield measurements indicate nearly quantitative SF in thin films of both chromophores in highly crystalline solvent-vapor-annealed films: 170 ± 20% for 1 and 200 ± 30% for 2. These results show that significantly different crystal morphologies of the same chromophore can both result in high-efficiency SF provided that the energetics are favorable.
AB - Two terrylene chromophores, 2,5,10,13-tetra(tert-butyl)terrylene (1) and 2,5-di(tert-butyl)terrylene (2), were synthesized and studied to determine their singlet exciton fission (SF) efficiencies. Compound 1 crystallizes in one-dimensional stacks, whereas 2 packs in a slip-stacked, herringbone pattern of dimers motif. Strongly quenched fluorescence and rapid singlet exciton decay dynamics are observed in vapor-deposited thin films of 1 and 2. Phosphorescence measurements on thin films of 1 and 2 show that SF is only 70 meV endoergic for these chromophores. Femtosecond transient absorption experiments using low laser fluences on these films reveal rapid triplet exciton formation for both 1 (τ = 120 ± 10 ps) and 2 (τ = 320 ± 20 ps) that depends strongly on film crystallinity. The transient absorption data are consistent with formation of an excimer state prior to SF. Triplet exciton yield measurements indicate nearly quantitative SF in thin films of both chromophores in highly crystalline solvent-vapor-annealed films: 170 ± 20% for 1 and 200 ± 30% for 2. These results show that significantly different crystal morphologies of the same chromophore can both result in high-efficiency SF provided that the energetics are favorable.
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U2 - 10.1021/acs.jpca.5b02719
DO - 10.1021/acs.jpca.5b02719
M3 - Article
VL - 119
SP - 4151
EP - 4161
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 18
ER -