The single-molecule magnet (SMM) properties of a series of ferrocenium complexes, [Fe(η5 -C5 R5 )2 ]+ (R=Me, Bn), are reported. In the presence of an applied dc field, the slow dynamics of the magnetization in [Fe(η5 -C5 Me5 )2 ]BArF are revealed. Multireference quantum mechanical calculations show a large energy difference between the ground and first excited states, excluding the commonly invoked, thermally activated (Orbach-like) mechanism of relaxation. In contrast, a detailed analysis of the relaxation time highlights that both direct and Raman processes are responsible for the SMM properties. Similarly, the bulky ferrocenium complexes, [Fe(η5 -C5 Bn5 )2 ]BF4 and [Fe(η5 -C5 Bn5 )2 ]PF6 , also exhibit magnetization slow dynamics, however an additional relaxation process is clearly detected for these analogous systems.
Keywords: ab initio calculations; electronic structure; magnetic properties; metallocenes; single-molecule magnets.
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