Electron transfer properties of non-alternant, substituted compounds related to fluoranthene. Experimental determination and theoretical modeling of electrochemical oxidation and reduction potentials in non-aqueous solution
✍ Scribed by L. Kraig Steffen; Benjamin F. Plummer; Tala L. Braley; W. Greg Reese; Kathryn Zych; Gregory Van Dyke; Michael Gill
- Publisher
- John Wiley and Sons
- Year
- 1997
- Tongue
- English
- Weight
- 152 KB
- Volume
- 10
- Category
- Article
- ISSN
- 0894-3230
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✦ Synopsis
The oxidation and reduction potentials of a series of related even non-alternant derivatives of 7,14-disubstituted acenaphth[1,2-k] fluoranthenes, and also fluoranthene, 7,10-diphenylfluoranthene and 8,9-dihydrodiindeno[1,2-j;2Ј,1Ј-] fluoranthene, were determined in organic solvents by cyclic voltammetry. The effects of steric hindrance on conjugation of the substituents with the central polycyclic aromatic hydrocarbon nucleus were evaluated. The semi-empirical molecular orbital calculation programs OMEGAMO, Extended H ückel, AM1 and PM3 were used to obtain optimal geometries and calculated HOMO and LUMO energies. As a further refinement, COSMO solvation was included in the AM1 calculations. The redox properties were correlated with data derived from the various semi-empirical calculations and the quality of these correlations is discussed. Inclusion of solvation energies in the computed molecular orbital energies results in a significant improvement in the correlation between observed and calculated oxidation potentials.