© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. We investigated the electronic properties of the molecular magnetic nanoto-ruses [Fe III 10 Ln III 10 (Me-tea) 10 (Me-teaH) 10 (NO 3 ) 10 ], examining the dependence on the lanthanide (Ln) of both the intra and intermolecular electronic channels. Using femtosecond absorption spectroscopy we show that the intramolecular electronic channels follow a three-step process, which involves vibrational cooling and crossing to shallow states, followed by recombination. A comparison with the energy gaps showed a relationship between trap efficiency and gaps, indicating that lanthanide ions create trap states to form excitons after photo-excitation. Using high-resistance transport measurements and scaling techniques, we investigated the intermolecular transport, demonstrating the dominant role of surface-limited transport channels and the presence of different types of charge traps. The intermolecular transport properties can be rationalized in terms of a hopping model, and a connection is provided to the far-IR spectroscopic properties. Comparison between intra and intermolecular processes highlights the role of the excited electronic states and the recombination processes, showing the influence of Kramers parity on the overall mobility.
