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- Title
Resonance Raman Spectra and Structures of Ni-Complexes of Octaalkylporphyrins in the Ground and Excited States.
- Authors
Terekhov, S. N.; Ivashin, N. V.
- Abstract
Quantum-chemical modeling of the structure and vibrational states of 4-coordinate Ni-complexes of octaalkylporphyrins (Ni–OAP) in the ground and 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 the 3(dz2, dx2–y2)configuration was attributed to the experimental spectrum obtained with a delay of ~2 ps after excitation and that recorded during pulsed nanosecond excitation in the saturation regime. The calculated data indicated the presence in the Ni–OEP solution of many conformers differing in the amount of macrocycle ruffling, which led to line broadening in the RRS. The absence of spectral signs of the 3(π, π*) state in the relaxation kinetics of the electronic excitation energy of Ni–OAP was shown to be due possibly to the lack of a local minimum in this state, in contrast to the corresponding porphyrin complexes of Cu, Zn, and Pd with large metal ionic radii. The effect of steric crowding for mono-meso-methyl-substituted Ni(II)etioporphyrins on the frequencies of structurally sensitive vibrations ν10, ν2, ν3, and ν4 in RRS in the ground and excited 3(dz2, dx2–y2) state was studied. The transition into the 3(dz2, dx2–y2) electronic configuration was shown to be accompanied by a significant decrease in the macrocycle ruffling deformation.
- Subjects
RESONANCE Raman effect; EXCITED states; METALLOPORPHYRINS; ELECTRON configuration; ELECTRONIC excitation; RAMAN scattering; COPPER
- Publication
Journal of Applied Spectroscopy, 2023, Vol 90, Issue 3, p499
- ISSN
0021-9037
- Publication type
Article
- DOI
10.1007/s10812-023-01559-x