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A combination of Raman spectroscopy and density functional theory calculations is used to describe the structural and spectroscopic properties of the different isomeric cations of diferrocenyl quaterthiophenes. Isomerisation of the thienyl β-positions provides site selective oxidation, which gives rise to species that can interconvert by moving the charge over the bridge. The spectroscopic study allows us to describe a sequence of stationary trapped cationic, either ferrocenyl or thienyl, states which constitutes an energy cascade of accessible sites through which the charge transfer can proceed.