Triplet Excited State Energies
and Phosphorescence
Spectra of (Bacterio)Chlorophylls
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Abstract
(Bacterio)Chlorophyll
((B)Chl) molecules play a major role in photosynthetic
light-harvesting proteins, and the knowledge of their triplet state
energies is essential to understand the mechanisms of photodamage
and photoprotection, as the triplet excitation energy of (B)Chl molecules
can readily generate highly reactive singlet oxygen. The triplet state
energies of 10 natural chlorophyll (Chl <i>a</i>, <i>b</i>, <i>c</i><sub>2</sub>, <i>d</i>) and
bacteriochlorophyll (BChl <i>a</i>, <i>b</i>, <i>c</i>, <i>d</i>, <i>e</i>, <i>g</i>) molecules and one bacteriopheophytin (BPheo <i>g</i>)
have been directly determined via their phosphorescence spectra. Phosphorescence
of four molecules (Chl <i>c</i><sub>2</sub>, BChl <i>e</i> and <i>g</i>, BPheo <i>g</i>) was
characterized for the first time. Additionally, the relative phosphorescence
to fluorescence quantum yield for each molecule was determined. The
measurements were performed at 77K using solvents providing a six-coordinate
environment of the Mg<sup>2+</sup> ion, which allows direct comparison
of these (B)Chls. Density functional calculations of the triplet state
energies show good correlation with the experimentally determined
energies. The correlation determined computationally was used to predict
the triplet energies of three additional (B)Chl molecules: Chl <i>c</i><sub>1</sub>, Chl <i>f</i>, and BChl <i>f</i>