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. 2013 Mar 14;117(10):2160-8.
doi: 10.1021/jp312376k. Epub 2013 Mar 6.

Polarization and symmetry of electronic transitions in long fluorescence lifetime triangulenium dyes

Erling Thyrhaug  1 , Thomas Just Sørensen, Ignacy Gryczynski, Zygmunt Gryczynski, Bo W Laursen
Affiliations

Polarization and symmetry of electronic transitions in long fluorescence lifetime triangulenium dyes

Erling Thyrhaug et al. J Phys Chem A. .

Abstract

To fully exploit the capabilities of fluorescence probes in modern experiments, where advanced instrumentation is used to probe complex environments, other photophysical properties than emission color and emission intensity are monitored. Each dye property can be addressed individually as well as collectively to provide in-depth information unavailable from the standard intensity measurements. Dyes with long emission lifetimes and strongly polarized transitions enable the monitoring of lifetime changes as well as emission polarization (anisotropy). Thus experiments can be designed to follow slow dynamics. The UV and visible electronic transitions of a series of red-emitting dyes based on the triangulenium motif are investigated. We resolve overlapping features in the spectra and assign the orientation of the transition moments to the molecular axes. The result is the complete Jablonski diagram for the UV and visible spectral region. The symmetries of the studied dyes are shown to have a large influence on the optical response, and they are clearly separated into two groups of symmetry by their photophysical properties. The C(2v) symmetric dyes, azadioxatriangulenium (ADOTA(+)) and diazaoxatriangulenium (DAOTA(+)), have high emission anisotropies, fluorescence lifetimes around 20 ns, and fluorescence quantum yields of ∼50%. The trioxatriangulenium (TOTA(+)) and triazatriangulenium (TATA(+)) dyes-nominally of D(3h) symmetry-have fluorescence lifetimes around 10 ns lifetimes and fluorescence quantum yields of 10-15%. However, the D(3h) symmetry is shown to be lowered to a point group, where the axes transform uniquely such that the degeneracy of the E' states is lifted.

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Figures

Figure 1
Figure 1
The molecular structure of the nitrogen an oxygen containing triangulenium dyes. Top row, from left: TOTA+, ADOTA+, DAOTA+, and TATA+. Bottom row from left: A-TOTA+, A-ADOTA+, and H-TOTA (all triangulenium dyes with donor substituents in the para positions).
Figure 2
Figure 2
Absorption (full line) and emission (dashed line) spectra of the triangulenium dyes in acetonitrile solution.
Figure 3
Figure 3
Excitation and emission spectra of ADOTA+ (top) and DAOTA+ (bottom) in a glycerol glass at 190 K. Excitation anisotropy spectra (565 nm and 590 nm detection wavelength respectively) and emission anisotropy spectra (525 nm and 540 nm excitation wavelength respectively) are superimposed on the excitation and emission spectra.
Figure 4
Figure 4
Reduced absorption spectra of ADOTA+ (top) and DAOTA+ (bottom) in stretched PVA film. The molecular z-axis is defined to be parallel to the stretching direction.
Figure 5
Figure 5
Isotropic excitation and emission spectra and fundamental anisotropies of TOTA+ (top) and TATA+ (bottom) in glycerol glass at 190 K.
Figure 6
Figure 6
Reduced excitation spectra of TOTA+ (top) and TATA+ (bottom) in glycerol glass at 190 K. The emission dipole is arbitrarily set to be parallel to the z-axis.
Figure 7
Figure 7
Jablonski diagram describing the first 4 transitions in the triangulenium dyes. The degenerate transitions of TOTA+ and TATA+ are split, and the states are here designated under the assumption that the nitrogen/oxygen on the remaining axis of symmetry is the stronger electron donor (ADOTA-like). If the donor strength is weaker the labels on the states will be reversed (DAOTA-like)
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