We report transport measurements through a single-molecule magnet, the Mn 12 derivative Mn 12 O 12 O 2 C-C 6 H 4 -SAc 16 H 2 O 4 , in a single-molecule transistor geometry. Thiol groups connect the molecule to gold electrodes that are fabricated by electromigration. Striking observations are regions of complete current suppression and excitations of negative differential conductance on the energy scale of the anisotropy barrier of the molecule. Transport calculations, taking into account the high-spin ground state and magnetic excitations of the molecule, reveal a blocking mechanism of the current involving nondegenerate spin multiplets.

Incorporation of a third, gate electrode in the device geometry of molecular junctions is necessary to identify the transport mechanism. At present, the most popular technique to fabricate three-terminal molecular devices makes use of electromigration. Although it is a statistical process, we show that control over the gap resistance can be obtained. A detailed analysis of the current-voltage characteristics of gaps without molecules, however, shows that they reveal features that can mistakenly be attributed to molecular transport. This observation raises questions about which gaps with molecules can be disregarded and which not. We show that electrical characteristics can be controlled by the rational design of the molecular bridge and that vibrational modes probed by electrical transport are of potential interest as molecular fingerprints.