Excited singlet states of covalently bound, cofacial dimers and trimers of perylene-3,4: 9,10-bis(dicarboximide)s

Jovan M. Giaimo, Jenny V. Lockard, Louise E. Sinks, Amy M. Scott, Thea M. Wilson, Michael R Wasielewski

Research output: Contribution to journalArticle

184 Citations (Scopus)

Abstract

Perylene-3,4:9,10-bis(dicarboximide) (PDI) and its derivatives are robust organic dyes that strongly absorb visible light and display a strong tendency to self-assemble into ordered aggregates, having significant interest as photoactive materials in a wide variety of organic electronics. To better understand the nature of the electronics states produced by photoexcitation of such aggregates, the photophysics of a series of covalent, cofacially oriented, π-stacked dimers and trimers of PDI and 1,7-bis(3′,5′-di-i- butylphenoxy)perylene-3,4: 9,10-bis(dicarboximide) (PPDI) were characterized using both time-resolved absorption and fluorescence spectroscopy. The covalent linkage between the chromophores was accomplished using 9,9-dimethylxanthene spacers. Placing n-octyl groups on the imide nitrogen atoms at the end of the PDI chromophores not attached to the xanthene spacer results in PDI dimers having near optimal π-stacking, leading to formation of a lowenergy excimer-like state, while substituting the more sterically demanding 12-tricosanyl group on the imides causes deviations from the optimum that result in slower formation of an excimer-like excited state having somewhat higher energy. By comparison, PPDI dimers having terminal n-octyl imide groups have two isomers, whose photophysical properties depend on the ability of the phenoxy groups at the 1,7-positions to modify the π stacking of the PPDI molecules. In general, disruption of optimal π-stacking by steric interactions of the phenoxy side groups results in excimer-like states that are higher in energy. The corresponding lowest excited singlet states of the PDI and PPDI trimers are dimer-like in nature and suggest that structural distortions that accompany formation of the trimers are sufficient to confine the electronic interaction on two chromophores within these systems. This further suggests that it may be useful to build into oligomeric PDI and PPDI systems some degree of flexibility that allows the structural relaxations necessary to promote electronic interactions between multiple chromophores.

Original languageEnglish
Pages (from-to)2322-2330
Number of pages9
JournalJournal of Physical Chemistry A
Volume112
Issue number11
DOIs
Publication statusPublished - Mar 20 2008

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Perylene
Chromophores
Imides
trimers
Excited states
Dimers
dimers
chromophores
imides
excimers
excitation
electronics
Xanthenes
spacers
Structural relaxation
Photoexcitation
Fluorescence spectroscopy
Electronic states
Absorption spectroscopy
Isomers

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Excited singlet states of covalently bound, cofacial dimers and trimers of perylene-3,4 : 9,10-bis(dicarboximide)s. / Giaimo, Jovan M.; Lockard, Jenny V.; Sinks, Louise E.; Scott, Amy M.; Wilson, Thea M.; Wasielewski, Michael R.

In: Journal of Physical Chemistry A, Vol. 112, No. 11, 20.03.2008, p. 2322-2330.

Research output: Contribution to journalArticle

Giaimo, Jovan M. ; Lockard, Jenny V. ; Sinks, Louise E. ; Scott, Amy M. ; Wilson, Thea M. ; Wasielewski, Michael R. / Excited singlet states of covalently bound, cofacial dimers and trimers of perylene-3,4 : 9,10-bis(dicarboximide)s. In: Journal of Physical Chemistry A. 2008 ; Vol. 112, No. 11. pp. 2322-2330.
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abstract = "Perylene-3,4:9,10-bis(dicarboximide) (PDI) and its derivatives are robust organic dyes that strongly absorb visible light and display a strong tendency to self-assemble into ordered aggregates, having significant interest as photoactive materials in a wide variety of organic electronics. To better understand the nature of the electronics states produced by photoexcitation of such aggregates, the photophysics of a series of covalent, cofacially oriented, π-stacked dimers and trimers of PDI and 1,7-bis(3′,5′-di-i- butylphenoxy)perylene-3,4: 9,10-bis(dicarboximide) (PPDI) were characterized using both time-resolved absorption and fluorescence spectroscopy. The covalent linkage between the chromophores was accomplished using 9,9-dimethylxanthene spacers. Placing n-octyl groups on the imide nitrogen atoms at the end of the PDI chromophores not attached to the xanthene spacer results in PDI dimers having near optimal π-stacking, leading to formation of a lowenergy excimer-like state, while substituting the more sterically demanding 12-tricosanyl group on the imides causes deviations from the optimum that result in slower formation of an excimer-like excited state having somewhat higher energy. By comparison, PPDI dimers having terminal n-octyl imide groups have two isomers, whose photophysical properties depend on the ability of the phenoxy groups at the 1,7-positions to modify the π stacking of the PPDI molecules. In general, disruption of optimal π-stacking by steric interactions of the phenoxy side groups results in excimer-like states that are higher in energy. The corresponding lowest excited singlet states of the PDI and PPDI trimers are dimer-like in nature and suggest that structural distortions that accompany formation of the trimers are sufficient to confine the electronic interaction on two chromophores within these systems. This further suggests that it may be useful to build into oligomeric PDI and PPDI systems some degree of flexibility that allows the structural relaxations necessary to promote electronic interactions between multiple chromophores.",
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