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Effects of heavy central metal on the ground and excited states of chlorophyll

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Abstract

Chlorophylls, owing to their adjustable π-electron system and intense, well-separated electronic transitions, can serve as convenient intrinsic spectroscopic probes of ligand–metal center interactions. They are also interesting for their photosensitizing properties. In order to examine the heavy-atom effects on the chlorophyll triplet state, a key intermediate in chlorophyll–photosensitized reactions, the synthesis of a novel Pt(II)-substituted chlorophyll a was carried out, and the effects of the substitution on steady-state and transient photophysical properties of chlorophyll were studied by absorption and fluorescence spectroscopies, and by laser flash photolysis. The presence of highly electronegative platinum as the central ion increases the energies of the chlorophyll main absorption transitions. As laser flash photolysis experiments show, in air-equilibrated solutions, chlorophyll triplets are efficiently quenched by molecular oxygen. Interestingly, this quenching by oxygen is more effective with metal-containing pigments, in spite of the increased spin–orbit coupling, introduced with the central metals. This points to occurrence of nonspecific interactions of molecular oxygen with metallochlorophylls. The differences in the effects exerted on the pigment triplet by the central metal become distinct after the removal of oxygen. The lifetime of a Pt-chlorophyll triplet remains very short, in the range of only a few microseconds, unlike in the free-base and Mg- and Zn-substituted chlorophylls. Such drastic shortening of the triplet lifetime can be attributed to a large heavy-atom effect, implying that strong interactions must occur between the central Pt(II) ion and the chlorophyll macrocycle, which lead to a more efficient spin–orbit coupling in Pt-chlorophyll than in Pt-porphyrins.

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Abbreviations

BChl:

Bacteriochlorophyll

BChla:

Bacteriochlorophyll a

Chl:

Chlorophyll

Chla:

Chlorophyll a

DEAE:

(Diethylamino)ethyl

F28TPP:

Perfluorinated tetraphenylporphyrin

HP:

Hematoporphyrin

HPLC:

High-performance liquid chromatography

ISC:

Intersystem crossing

Mg-Chla:

Magnesium-substituted chlorophyll a

PDT:

Photodynamic therapy

Pheo:

Pheophytin a

Pt-Chla:

Platinum-substituted chlorophyll a

TPP:

Tetraphenylporphyrin

Zn-Chla:

Zinc-substituted chlorophyll a

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Acknowledgements

The authors thank A. Dudkowiak for helpful discussions. The project was supported by research grants from the Jagiellonian University (CRBW 2002/2003) and KBN (2 P05 F04 628).

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Authors and Affiliations

  1. Faculty of Chemistry, Kraków, Poland

    Agnieszka Drzewiecka-Matuszek, Agnieszka Skalna, Andrzej Karocki & Grażyna Stochel

  2. Faculty of Biotechnology, Jagiellonian University, Kraków, Poland

    Leszek Fiedor

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  1. Agnieszka Drzewiecka-Matuszek
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  2. Agnieszka Skalna
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  3. Andrzej Karocki
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  4. Grażyna Stochel
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  5. Leszek Fiedor
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Correspondence to Grażyna Stochel.

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Drzewiecka-Matuszek, A., Skalna, A., Karocki, A. et al. Effects of heavy central metal on the ground and excited states of chlorophyll. J Biol Inorg Chem 10, 453–462 (2005). https://doi.org/10.1007/s00775-005-0652-6

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