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Resonance Raman Spectra and the Structure of Ni-Complexes of Octaalkylporphyrins in the Ground and Photoexcited States
Abstract
Quantum-chemical modeling of the structure and vibrational states of 4-coordinated Ni-complexes of octaalkylporphyrins (Ni-OAP) in the ground and in a series of (d, d), (π, d) and (π, π) excited states has been carried out. The calculated resonance Raman spectrum (RRS) of Ni(II)-octaethylporphyrin (Ni-OEP) in 3(dz2, dx2-y2) configuration is attributed to the experimental spectrum obtained at a delay of ~2 ps after excitation, as well as the spectrum recorded during pulsed nanosecond excitation in the saturation regime. The calculated data indicate the presence in the Ni-OEP solution of a large number of conformers that differ in the amount of macrocycle corrugation, which leads to line broadening in the RRS spectra. It is shown that the absence of spectral signs of 3(π, π*) state in the relaxation kinetics of the electronic excitation energy of Ni-OAP may be due to the fact that, in contrast to the corresponding Cu-, Zn-, and Pd-complexes of porphyrins with large ionic radius of the metal, for them in this state there is no local minimum. The effect of steric crowding for the mono-meso-methyl substituted Ni(II)-ethioporphyrins on the frequencies of structurally sensitive vibrations v10, v2, v3, v4 in the RRS spectra in the ground and excited 3(dz2, dx2-y2) state is studied. It is shown that the transition to the electronic configuration 3(dz2, dx2-y2) is accompanied by a significant de-crease in the macrocycle corrugation deformation.
About the Authors
S. N. Terekhov
B.I. Stepanov Institute of Physics of the National Academy of Sciences of Belarus
Belarus
Belarus
Minsk
N. V. Ivashin
B.I. Stepanov Institute of Physics of the National Academy of Sciences of Belarus
Belarus
Belarus
Minsk
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Review
For citations:
Terekhov S.N., Ivashin N.V. Resonance Raman Spectra and the Structure of Ni-Complexes of Octaalkylporphyrins in the Ground and Photoexcited States. Zhurnal Prikladnoii Spektroskopii. 2023;90(3):376-384. (In Russ.)
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