Controllable Electron Transfer in Mixed-Valence Bridged Norbornylogous Compounds: Ab Initio Calculation Combined with a Parametric Model and Through-Bond and Through-Space Interpretation

In the context of a computationally guided approach to the controllable electron transfer in mixed-valence (MV) systems, in this article, we study the electron transfer (ET) in the series of oxidized norbornadiene C7H8 (I) and its polycyclic derivatives, C12H12 (II) C17H16, (III), C27H24 (IV), and C32H28 (V), with variable lengths of the bridge connecting redox sites. The work combines an ab initio CASSCF evaluation of the electronic structure of systems I-V with the parametric description in the framework of the biorbital two-mode vibronic model. The model involves coupling with the breathing mode and intercenter vibration modulating the distances between the redox fragments. The ab initio calculations were performed for two types of optimized structures of I-V: (a) charge-localized global minimum (C-s) and (b) symmetric configuration (C-2v) with the delocalized charge. This allows one to estimate the potential barrier separating charge-localized configurations as well as vibronic coupling parameters and the electron transfer integral. Along with the adiabatic approach, the quantum-mechanical analysis of the vibronic levels has been applied to precisely estimate the quantum effect of tunneling splitting. We estimate the through-space and through-bond contributions to the parameters interrelated with the charge transfer (CT). The through-space effect proves to be a major factor of ET at a short distance between the redox centers, whereas the through-bond contribution is dominant at a long distance. Vibronic coupling under the condition of through-space ET leads to the localization of the positive charge on the pi-chromophore, while the through-bond component of ET results in compensating sigma-shifts and subsequent charge delocalization over the bridge. The limitations of the parametric approach were discussed in the context of the two components contributing to the ET. Particularly, the bridge polarization in the course of through-bond ET proves to be beyond the basis of the employed parametric model.

Automated summary

In this study, the controllable electron transfer in mixed-valence systems was investigated computationally. The electron transfer in a series of oxidized norbornadiene and its derivatives was studied. The through-space effect was found to be the major factor in electron transfer at short distances between the redox centers, while the through-bond contribution dominated at long distances.