We found a match
Your institution may have access to this item. Find your institution then sign in to continue.
- Title
Study of the structure and spectral properties of dianions of Zn complexes of porphyrins by the method of density functional theory.
- Authors
Parkhots, O. P.; Ivashin, N. V.
- Abstract
The structure, solvation energies, and electronic absorption spectra of products corresponding to the second stage of reduction of Zn porphin (Zn-P) with metallic sodium are calculated using methods of density functional theory. Calculated solvation energies of free and bound ions make it possible to assume that, in commonly used aprotic solvents, reduction products form [2Na+ · Zn-P2−] anion-cation contact complexes. The relative energies of the four stable isomers [2Na+ · Zn-P2−] detected in the gas phase and solvents are considerably different. The arrangement of Na+ on different sides of the macrocycle and along the NN axis favors the interaction with the solvent and stabilization in the solution. This conclusion is consistent with the data of calculations of electronic absorption spectra and of modeling of the spectral manifestations of the electron photodetachment from dianions of Zn-tetraphenylporphyrin (Zn-TPP) in frozen matrices. The behavior of the calculated transitions in the series of neutral and charged forms of Zn-P and Zn-TPP is well consistent with experimental data. Despite the fact that the spectral properties of the neutral and dianionic forms of Zn-P and Zn-TPP in the visible range are similar, the nature of their excited states is different.
- Subjects
PORPHYRINS; PHOTODETACHMENT threshold spectroscopy; DENSITY functionals; MATRICES (Mathematics); NUCLEAR isomers; MACROCYCLIC compounds
- Publication
Optics & Spectroscopy, 2009, Vol 106, Issue 2, p213
- ISSN
0030-400X
- Publication type
Article
- DOI
10.1134/S0030400X09020106