Theoretical Study and Structural Relationships of Free Energies of Electron Transfer, Electrochemical Properties and Electron Transfer Kinetics of Ferrocene Derivatives with Fullerenes in Nanostructures of [(R)2Cp2-Fe].Cn Supramolecular Complexes

Abstract

Ferrocene (Cp2-Fe) and its derivatives are part of a broad-spectrum of organometallic compounds that are commonly used in electronics and semiconductors. Fullerenes are a family of carbon allotropes composed entirely of carbon in the form of spheres, ellipsoids and cylinders. Various empty carbon fullerenes (Cn) have been obtained and investigated. The Cp2-Fe derivatives have exhibited important electron-transfer properties. Topological indices have been proposed to correlate structures with properties. They have been successfully employed to construct effective and useful mathematical methods to establish clear relationships between structural data and the physical properties of these materials. In this study, the number of carbon atoms in the fullerenes was used as an index to establish a relationship between the structures of ferrocenyl derivatives (1–15), ferrocenyl fullerene complexes 1–15 (the most well-known redox systems) and fullerenes Cn (n = 60, 70, 76, 82 and 86) A-1 to O-5, which are commonly denoted as [Fc-x].Cn. The Rehm-Weller equation was applied to build the relationship between the structures and the free energies for electron transfer (ΔGet(1) to ΔGet(4) ) of the complexes [Fc-x].Cn (A-1 to O-5). The calculations are presented for the four reduction potentials ( Red.E1 to Red.E4 ) of the fullerenes Cn . The reduction potentials of the fullerenes Cn have been applied to calculate the four free energies of electron transfer (ΔGet(1) to ΔGet(4) ) of supramolecular complexes [Fc-x].Cn (A-1 to O-5). Based on Marcus theory and Planck's equation, the first four free activation energies of electron transfer and the wavelengths (ΔGet(1) # to ΔGet(4) # and λ et , n = 1–4, respectively) for the photoelectron transfer process were also calculated for [Fc-x].Cn (A-1 to O-5).