Abstract
We report the synthesis and photophysical characterization of a multichromophore array, (Z3PN)4PDI, consisting of four zinc 5-phenyl-10,15,20-tri(n-pentyl)porphyrins (Z3PN) attached to the 1,7,N,N′-positions of perylene-3,4:9,10-bis(dicarboximide) (PDI). The dynamics of energy and charge transport within this system were compared to those of two model compounds, N,N′-(Z3PN)2PDI and 1,7-(Z3PN)2PDI. The symmetry of the lowest unoccupied and highest occupied molecular orbitale of PDI results in significantly different electronic couplings between Z3PN and PDI when they are connected at the 1,7-positions vs the N,N′-positions of PDI. This results in two distinct pathways for electron transfer in (Z3PN)4PDI. Using a combination of metal-ligand binding with the bidentate ligand 1,4-diazabicyclo[2.2.2.]-octane (DABCO) and π-π stacking, (Z3PN4)PDI forms a supramolecular assembly, [[(Z3PN)4PDI]2-DABCO4]2, in toluene solution. The structure of this hierarchical assembly is characterized with the use of solution-phase X-ray scattering techniques and demonstrates both efficient light harvesting and facile charge separation and transport using multiple pathways.
| Original language | English |
|---|---|
| Pages (from-to) | 3173-3181 |
| Number of pages | 9 |
| Journal | Journal of the American Chemical Society |
| Volume | 129 |
| Issue number | 11 |
| DOIs | |
| Publication status | Published - Mar 21 2007 |
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Cite this
Photoinitiated charge transport in supramolecular assemblies of a 1,7,N,N′-tetrakis(zinc porphyrin)-perylene-3,4 : 9,10-bis(dicarboximide). / Kelley, Richard F.; Shin, Won Suk; Rybtchinski, Boris; Sinks, Louise E.; Wasielewski, Michael R.
In: Journal of the American Chemical Society, Vol. 129, No. 11, 21.03.2007, p. 3173-3181.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Photoinitiated charge transport in supramolecular assemblies of a 1,7,N,N′-tetrakis(zinc porphyrin)-perylene-3,4
T2 - 9,10-bis(dicarboximide)
AU - Kelley, Richard F.
AU - Shin, Won Suk
AU - Rybtchinski, Boris
AU - Sinks, Louise E.
AU - Wasielewski, Michael R
PY - 2007/3/21
Y1 - 2007/3/21
N2 - We report the synthesis and photophysical characterization of a multichromophore array, (Z3PN)4PDI, consisting of four zinc 5-phenyl-10,15,20-tri(n-pentyl)porphyrins (Z3PN) attached to the 1,7,N,N′-positions of perylene-3,4:9,10-bis(dicarboximide) (PDI). The dynamics of energy and charge transport within this system were compared to those of two model compounds, N,N′-(Z3PN)2PDI and 1,7-(Z3PN)2PDI. The symmetry of the lowest unoccupied and highest occupied molecular orbitale of PDI results in significantly different electronic couplings between Z3PN and PDI when they are connected at the 1,7-positions vs the N,N′-positions of PDI. This results in two distinct pathways for electron transfer in (Z3PN)4PDI. Using a combination of metal-ligand binding with the bidentate ligand 1,4-diazabicyclo[2.2.2.]-octane (DABCO) and π-π stacking, (Z3PN4)PDI forms a supramolecular assembly, [[(Z3PN)4PDI]2-DABCO4]2, in toluene solution. The structure of this hierarchical assembly is characterized with the use of solution-phase X-ray scattering techniques and demonstrates both efficient light harvesting and facile charge separation and transport using multiple pathways.
AB - We report the synthesis and photophysical characterization of a multichromophore array, (Z3PN)4PDI, consisting of four zinc 5-phenyl-10,15,20-tri(n-pentyl)porphyrins (Z3PN) attached to the 1,7,N,N′-positions of perylene-3,4:9,10-bis(dicarboximide) (PDI). The dynamics of energy and charge transport within this system were compared to those of two model compounds, N,N′-(Z3PN)2PDI and 1,7-(Z3PN)2PDI. The symmetry of the lowest unoccupied and highest occupied molecular orbitale of PDI results in significantly different electronic couplings between Z3PN and PDI when they are connected at the 1,7-positions vs the N,N′-positions of PDI. This results in two distinct pathways for electron transfer in (Z3PN)4PDI. Using a combination of metal-ligand binding with the bidentate ligand 1,4-diazabicyclo[2.2.2.]-octane (DABCO) and π-π stacking, (Z3PN4)PDI forms a supramolecular assembly, [[(Z3PN)4PDI]2-DABCO4]2, in toluene solution. The structure of this hierarchical assembly is characterized with the use of solution-phase X-ray scattering techniques and demonstrates both efficient light harvesting and facile charge separation and transport using multiple pathways.
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U2 - 10.1021/ja0664741
DO - 10.1021/ja0664741
M3 - Article
C2 - 17319659
AN - SCOPUS:33947431975
VL - 129
SP - 3173
EP - 3181
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 11
ER -