Spin Dynamics in the Negatively Charged Terbium (III) Bis-phthalocyaninato Complex

The experimental and theoretical study of the electron spin dynamics in the anionic form of a single-ion molecule magnet (SIMM), the bis-phthalocyaninato terbium (III) molecule [Pc2Tb]-[TBA]+, has been addressed by means of solid state 1H NMR spectroscopy. The magnetic properties of the caged Tb3+ metal center were investigated in a series of diamagnetically diluted preparations, where the excess of tetrabutylamonium bromide ([TBA]Br)n salt was used as diamagnetic matrix complement. We found that a high temperature activated spin dynamics characterizes the systems, which involved phonon-assisted transitions among the crystal field levels in qualitative agreements with literature results. However, the activation barriers in these processes range from 641 cm-1 for the diamagnetically diluted samples to 584 cm-1 for those undiluted; thus, they exhibit barriers 2-3 times larger than witnessed in earlier (230 cm-1) reports (e.g., Ishikawa, N.; Sugita, M.; Ishikawa, T.; Koshihara, S.; Kaizu, Y. J. Am. Chem. Soc. 2003, 125, 8694-8695). At cryogenic temperatures, fluctuations are driven by tunneling processes between the m=+6 and -6 low-energy levels. We found that the barrier ∆ and the tunneling rates change from sample to sample and especially the diamagnetically diluted [Pc2Tb]- molecules appear affected by the sample’s magneto/thermal history. These observations emphasize that matrix arrangements around [Pc2Tb]- can appreciably alter the splitting of the crystal field levels, its symmetry, and hence, the spin dynamics. Therefore, understanding how small differences in molecular surroundings (as for instance occurring by depositing on surfaces) can trigger substantial modifications in the SIMM property is of utmost importance for the effective operation of such molecules for single-molecule data storage, for example.