Computational study of topological effects on intramolecular electron transfer in mixed-valence compounds

The constrained density functional theory (CDFT) was used to investigate the topological effects on intramolecular electron transfer processes that have been reported in previous experimental work [Inorg. Chem., 1997, 36 (22), pp 5037–5049]. The computation mainly focused on three isomers of diferrocenylbenzenes (ortho, para, and meta) and 5-substituted derivatives of m-diferrocencylbenzenes with R = NH₂, Cl, CH₃, CN, NO₂, NeCH₃)₃³⁺, and N₂⁺. The influence of a third group R′ (R′ = NH₂ and N₂⁺) was introduced to the ortho and para isomers. The calculations were compared with the experimental results. The relation between the substituted functional groups and the effectiveness of intramolecular electron transfer was discussed on the basis of CDFT computational results.