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- Title
Out-of-plane C<sub> m </sub>H vibrations and electronic structure of Zn complexes of porphyrins and their π anions.
- Authors
Parkhots, O. P.; Ivashin, N. V.
- Abstract
Based on the calculation of frequencies of the normal vibrations of Zn complexes of octaalkylporphyrins (Zn-OAPs), Zn porphin (Zn-P), and their meso-deuterated derivatives by the method of density functional theory (B3LYP/6–31G( d, B3LYP/6–311+G( d)), a new interpretation of C m H(D) out-of-plane deformation vibrations of porphyrins is proposed. It is shown that the vibration patterns of these modes are characterized by high contributions (>90%) of the coordinates of displacement out of the macrocycle plane of the H(D) atoms in meso positions. At the same time, a small change in the vibration pattern of such a mode in the d 4 isotopomer (∼5%) is accompanied by a large change in its intensity. The geometry of free π anionic forms of Zn-OAPs and Zn-P and their complexes with cations Na+ and K+ is optimized, and the normal vibrations of these compounds are calculated. A comparison with experimental IR spectra of solid samples shows that anion-cation complexes form under these conditions. The interaction with cations lowers the symmetry of the nuclear skeleton of reduced forms of Zn-OAPs, considerably decreases their charge, and markedly affects the structure of this skeleton and its vibrations.
- Subjects
PORPHYRINS; ELECTRONIC structure; FUNCTIONAL analysis; ANIONS; CATIONS; ZINC compounds
- Publication
Optics & Spectroscopy, 2006, Vol 101, Issue 2, p215
- ISSN
0030-400X
- Publication type
Article
- DOI
10.1134/S0030400X0608008X