Steps to demarcate the effects of chromophore aggregation and planarization in poly(phenyleneethynylene)s. 2. The photophysics of 1,4-diethynyl-2-fluorobenzene in solution and in crystals

Marcia Levitus, G. Zepeda, H. Dang, C. Godinez, T. A V Khuong, K. Schmieder, M. A. Garcia-Garibay

Research output: Contribution to journalArticle

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Abstract

Crystals of 1,4-bis(2-hydroxy-2-methyl-3-butynyl)-2-fluorobenzene 4 have a rich packing structure with four distinct molecules in the unit cell. A complex hydrogen bonding network results in the formation of cofacial trimers, cofacial dimers, and monomers within the same unit cell. Given a remarkable opportunity to investigate the effect of aggregation on the photophysics of 1,4-diethynylbenzenes, we analyzed the absorption, diffuse reflectance, and emission spectra of compound 4 in solutions and in crystals. Diffuse reflectance and fluorescence excitation revealed a red-shifted absorption that is absent in dilute solution but becomes observable at high concentrations and low temperatures. The fluorescence emission in the solid state is dual with components assigned to monomers and aggregates. The excitation and emission assigned to the monomer are nearly identical in crystals and dilute solutions. The absorption and emission bands assigned to aggregates are broad and red-shifted by 60-80 nm. As expected for a sample with absorbers and emitters with different energies and incomplete equilibration, efficient monomer-to-aggregate energy transfer was observed by a proper selection of excitation wavelengths. The fluorescence quantum yield of 4 in solution is relatively low (ΦF = 0.15) and the singlet lifetime short (τF = 3.8 ns). A lower limit for the triplet yield of ΦT = 0.64 was determined indirectly in solution by 1O2 sensitization, and a relatively strong and long-lived phosphorescence was observed in low-temperature glasses and in crystals at 77 K.

Original languageEnglish (US)
Pages (from-to)3188-3195
Number of pages8
JournalJournal of Organic Chemistry
Volume66
Issue number9
DOIs
StatePublished - May 4 2001
Externally publishedYes

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Fluorobenzenes
Chromophores
Agglomeration
Crystals
Monomers
Fluorescence
Phosphorescence
Quantum yield
Dimers
Energy transfer
Hydrogen bonds
phenyleneethynylene
Glass
Wavelength
Temperature
Molecules

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Steps to demarcate the effects of chromophore aggregation and planarization in poly(phenyleneethynylene)s. 2. The photophysics of 1,4-diethynyl-2-fluorobenzene in solution and in crystals. / Levitus, Marcia; Zepeda, G.; Dang, H.; Godinez, C.; Khuong, T. A V; Schmieder, K.; Garcia-Garibay, M. A.

In: Journal of Organic Chemistry, Vol. 66, No. 9, 04.05.2001, p. 3188-3195.

Research output: Contribution to journalArticle

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abstract = "Crystals of 1,4-bis(2-hydroxy-2-methyl-3-butynyl)-2-fluorobenzene 4 have a rich packing structure with four distinct molecules in the unit cell. A complex hydrogen bonding network results in the formation of cofacial trimers, cofacial dimers, and monomers within the same unit cell. Given a remarkable opportunity to investigate the effect of aggregation on the photophysics of 1,4-diethynylbenzenes, we analyzed the absorption, diffuse reflectance, and emission spectra of compound 4 in solutions and in crystals. Diffuse reflectance and fluorescence excitation revealed a red-shifted absorption that is absent in dilute solution but becomes observable at high concentrations and low temperatures. The fluorescence emission in the solid state is dual with components assigned to monomers and aggregates. The excitation and emission assigned to the monomer are nearly identical in crystals and dilute solutions. The absorption and emission bands assigned to aggregates are broad and red-shifted by 60-80 nm. As expected for a sample with absorbers and emitters with different energies and incomplete equilibration, efficient monomer-to-aggregate energy transfer was observed by a proper selection of excitation wavelengths. The fluorescence quantum yield of 4 in solution is relatively low (ΦF = 0.15) and the singlet lifetime short (τF = 3.8 ns). A lower limit for the triplet yield of ΦT = 0.64 was determined indirectly in solution by 1O2 sensitization, and a relatively strong and long-lived phosphorescence was observed in low-temperature glasses and in crystals at 77 K.",
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AU - Levitus, Marcia

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AU - Dang, H.

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AU - Schmieder, K.

AU - Garcia-Garibay, M. A.

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