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

Abstract

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, $\mathrm{N}{(\mathrm{C}{\mathrm{H}}_{\mathrm{3}})}_{\mathrm{3}}^{\mathrm{3}+}$, and ${\mathrm{N}}_{\mathrm{2}}^{+}$. The influence of a third group R’ (R’ = NH₂ and ${\mathrm{N}}_{\mathrm{2}}^{+}$) 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.

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Acknowledgements

This work was supported by the National Natural Science Foundation (No. CHE-1012479). The computations were performed using resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the US Department of Energy under Contract No. DE-AC02-05CH11231.

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