Intermolecular interaction of photoexcited Cu(/TMpy-P4) with water studied by transient resonance Raman and picosecond absorption spectroscopies

Sergei G. Kruglik, Vladimir V. Ermolenkov, Alexander G. Shvedko, Valentine A. Orlovich, Victor A. Galievsky, Vladimir S. Chirvony, Cees Otto, Pierre-Yves Turpin

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Abstract

A photoinduced complex between Cu(TMpy-P4) and water molecules, reversibly axially coordinated to the central metal, was observed in picosecond transient absorption and nanosecond resonance Raman experiments. This complex is rapidly created (τ1 = 15 ± 5 ps) in the excited triplet (π, π*) state of Cu-porphyrin, and the subsequent relaxation is proposed to proceed via two parallel pathways. One is fast and efficient (≥90% of molecules), and presumably involves a (π, d) charge-transfer state. The second pathway is slow (τ2 >> 1 ns), has a low quantum yield (≤10%) and involves the excited (d, d) state which is responsible for transient Raman features at ≈ 1553 cm−1 (ν2*) and ≈ 1347 cm−1 (ν4*), and for low-intensity long-lived transient absorption features.
Original languageEnglish
Pages (from-to)293-298
Number of pages6
JournalChemical physics letters
Volume270
Issue number3-4
DOIs
Publication statusPublished - 1997

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    Kruglik, S. G., Ermolenkov, V. V., Shvedko, A. G., Orlovich, V. A., Galievsky, V. A., Chirvony, V. S., ... Turpin, P-Y. (1997). Intermolecular interaction of photoexcited Cu(/TMpy-P4) with water studied by transient resonance Raman and picosecond absorption spectroscopies. Chemical physics letters, 270(3-4), 293-298. https://doi.org/10.1016/S0009-2614(97)00362-X