Photoinitiated charge transport in supramolecular assemblies of a 1,7,N,N′-tetrakis(zinc porphyrin)-perylene-3,4: 9,10-bis(dicarboximide)

Richard F. Kelley, Won Suk Shin, Boris Rybtchinski, Louise E. Sinks, Michael R Wasielewski

Research output: Contribution to journalArticle

120 Citations (Scopus)

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 languageEnglish
Pages (from-to)3173-3181
Number of pages9
JournalJournal of the American Chemical Society
Volume129
Issue number11
DOIs
Publication statusPublished - Mar 21 2007

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Perylene
Porphyrins
Charge transfer
Zinc
Ligands
Toluene
X ray scattering
Metals
X-Rays
Electrons
Light
zinc hematoporphyrin

ASJC Scopus subject areas

  • Chemistry(all)

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 journalArticle

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