Magnetic and redox properties in hydroxo- and alkoxo-bridged Fe(III) binuclear complexes: A density functional study
✍ Scribed by Andrea Caneschi; Fabrizia Fabrizi de Biani; Lars Kloo; Piero Zanello
- Publisher
- John Wiley and Sons
- Year
- 1999
- Tongue
- English
- Weight
- 458 KB
- Volume
- 72
- Category
- Article
- ISSN
- 0020-7608
No coin nor oath required. For personal study only.
✦ Synopsis
DFT calculations were carried out in order to deduce the dependence of Ž . magnetic coupling on the structure of doubly hydroxideralkoxide-bridged diiron III dimers. The broken-symmetry formalism was employed to calculate the magnetic exchange parameter J. The potential surfaces of the ground state display a geometrical Ž . minimum at an Fe-O H -Fe angle of 105Њ and Fe иии Fe distance of 3.2 A, in good agreement with experimental values. The calculated correlation between the magnetic coupling with the geometrical structure agrees well with the experimental literature data, although always overestimated. Electrochemical measurements show that a one-electron reduction is likely to cause dissociation into pseudooctahedral, monomeric subunits, and, consequently, no calculations were made for the reduced dimeric species.