Abstract
Excitation energy transfer in perylene-3,4:9,10-bis(dicarboximide) (PDI) aggregates is of interest for light-harvesting applications of this strongly absorbing and π-π stacking chromophore. Here we report the synthesis and characterization of two PDI dimers in which the chromophores are covalently linked by a redox-inactive triptycene bridge in orientations that are cofacial (1) and slip-stacked along their N-N axes (2). Femtosecond transient absorption experiments on 1 and 2 reveal rapid exciton delocalization resulting excimer formation. Cofacial π-π stacked dimer 1 forms a low-energy excimer state absorption (λmax = 1666 nm) in τ = ∼2 ps after photoexcitation. Inserting a phenyl spacer on the bridge to generate a slip-stacked PDI-PDI geometry in 2 results in a less stable excimer state (λmax = 1430 nm), which forms in τ = ∼12 ps due to decreased electronic coupling. The near-infrared (NIR) excimer absorption of cofacial dimer 1 is ∼120 meV lower in energy than that of slip-stacked dimer 2, further highlighting electronic differences between these states.
| Original language | English |
|---|---|
| Pages (from-to) | 23735-23742 |
| Number of pages | 8 |
| Journal | Physical Chemistry Chemical Physics |
| Volume | 16 |
| Issue number | 43 |
| DOIs | |
| Publication status | Published - Nov 21 2014 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Physics and Astronomy(all)
Cite this
Excimer formation in cofacial and slip-stacked perylene-3,4 : 9,10-bis(dicarboximide) dimers on a redox-inactive triptycene scaffold. / Margulies, Eric A.; Shoer, Leah E.; Eaton, Samuel W.; Wasielewski, Michael R.
In: Physical Chemistry Chemical Physics, Vol. 16, No. 43, 21.11.2014, p. 23735-23742.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Excimer formation in cofacial and slip-stacked perylene-3,4
T2 - 9,10-bis(dicarboximide) dimers on a redox-inactive triptycene scaffold
AU - Margulies, Eric A.
AU - Shoer, Leah E.
AU - Eaton, Samuel W.
AU - Wasielewski, Michael R
PY - 2014/11/21
Y1 - 2014/11/21
N2 - Excitation energy transfer in perylene-3,4:9,10-bis(dicarboximide) (PDI) aggregates is of interest for light-harvesting applications of this strongly absorbing and π-π stacking chromophore. Here we report the synthesis and characterization of two PDI dimers in which the chromophores are covalently linked by a redox-inactive triptycene bridge in orientations that are cofacial (1) and slip-stacked along their N-N axes (2). Femtosecond transient absorption experiments on 1 and 2 reveal rapid exciton delocalization resulting excimer formation. Cofacial π-π stacked dimer 1 forms a low-energy excimer state absorption (λmax = 1666 nm) in τ = ∼2 ps after photoexcitation. Inserting a phenyl spacer on the bridge to generate a slip-stacked PDI-PDI geometry in 2 results in a less stable excimer state (λmax = 1430 nm), which forms in τ = ∼12 ps due to decreased electronic coupling. The near-infrared (NIR) excimer absorption of cofacial dimer 1 is ∼120 meV lower in energy than that of slip-stacked dimer 2, further highlighting electronic differences between these states.
AB - Excitation energy transfer in perylene-3,4:9,10-bis(dicarboximide) (PDI) aggregates is of interest for light-harvesting applications of this strongly absorbing and π-π stacking chromophore. Here we report the synthesis and characterization of two PDI dimers in which the chromophores are covalently linked by a redox-inactive triptycene bridge in orientations that are cofacial (1) and slip-stacked along their N-N axes (2). Femtosecond transient absorption experiments on 1 and 2 reveal rapid exciton delocalization resulting excimer formation. Cofacial π-π stacked dimer 1 forms a low-energy excimer state absorption (λmax = 1666 nm) in τ = ∼2 ps after photoexcitation. Inserting a phenyl spacer on the bridge to generate a slip-stacked PDI-PDI geometry in 2 results in a less stable excimer state (λmax = 1430 nm), which forms in τ = ∼12 ps due to decreased electronic coupling. The near-infrared (NIR) excimer absorption of cofacial dimer 1 is ∼120 meV lower in energy than that of slip-stacked dimer 2, further highlighting electronic differences between these states.
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U2 - 10.1039/c4cp03107e
DO - 10.1039/c4cp03107e
M3 - Article
VL - 16
SP - 23735
EP - 23742
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 43
ER -