Prediction of the reduction potential of tris(2,2'-bipyridinyl)iron(III/II) derivatives.

摘要: The reduction potentials of a tris(2,2′-bipyridinyl)iron (III/II) and iron(III/II) couples complexed with 2,2′-bipyridinyl derivatives in acetonitrile are predicted using density functional theory. calculation protocol proposed by Kim et al. (Kim, J. Park, Y. S. Lee, Comput. Chem. 2013, 34, 2233) showing reliable performance for the potential is used. four kinds groups, methoxy group, methyl chlorine atom, cyanide substituted at ligands to examine electronic effect on potential. Electron donating/withdrawing analyzed comparing having different substituents same position. influence geometrical strain investigated. good correlation between experimental results calculated obtained. Not only general trend, but also detailed phenomena correctly reproduced. maximum deviation from value 0.083 V substitution position 4. mean absolute error seven 0.047 V. difference atom positions 4 5, 0.1 V, well described. CN Cl 0.318 0.228 5 obtained as 0.325 0.213 respectively. simple linear relation lowest unoccupied molecular orbital (LUMO) energy Fe(III) complexes solution R2 0.977. © 2014 Wiley Periodicals, Inc.