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Manifestation of Extracoordination in the Resonance Raman Spectra of Water‐Soluble Cation Co‐Porphyrins

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Abstract

Resonance Raman spectra (RRS) of Co(II)‐ and Co(III)‐5,10,15,20‐tetrakis(4‐N‐methylpyridinium)porphyrin ((CoII(Tmpy‐P4), and CoIII(TMPy‐P4)) in aqueous solutions at different pH as well as in organic solvents (methanol, ethanol, DMSO, DMF) are obtained. The increased sensitivity of the oscillation frequencies ν2, ν4, ν8, and ν6 — the “markers” of the oxidation state of a metal — to the nature of an axial ligand has been revealed. For CoIII(Tmpy‐P4), the shifts of the indicated frequencies in extracoordination have turned out to be twofold larger than those for CoII(Tmpy‐P4). The spectral effects observed are related to different electron influence of the extraligands on the π‐system of the porphyrin ring. In the case of Co(III)‐porphyrin, interaction of the d π‐orbitals of the metal and the e g *‐orbitals of the macrocycle is more efficient since its ionic radius is smaller than for the Co(II)‐complex. For CoIII(Tmpy‐P4), a linear correlation between the oscillation frequencies ν2, ν4, ν8, and ν6 and the experimental Gutmann parameters characterizing the electron‐acceptor properties of solvents is found.

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Authors and Affiliations

  1. Institute of Molecular and Atomic Physics, National Academy of Sciences of Belarus, 70 F. Skorina Ave., Minsk, 220072, Belarus

    S. N. Terekhov & V. S. Chirvonyi

  2. Université de Piérre et Marie Curie, Paris, France

    P.‐Y. Turpin

Authors
  1. S. N. Terekhov
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  2. V. S. Chirvonyi
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  3. P.‐Y. Turpin
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Correspondence to S. N. Terekhov.

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Terekhov, S.N., Chirvonyi, V.S. & Turpin, P. Manifestation of Extracoordination in the Resonance Raman Spectra of Water‐Soluble Cation Co‐Porphyrins. Journal of Applied Spectroscopy 69, 717–725 (2002). https://doi.org/10.1023/A:1021504912464

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