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Crystal lattice desolvation effects on the magnetic quantum tunneling of single-molecule magnets

2009; American Physical Society; Volume: 80; Issue: 9 Linguagem: Inglês

10.1103/physrevb.80.094408

1550-235X

Gage Redler, Christos Lampropoulos, Subhadeep Datta, Changhyun Koo, Theocharis C. Stamatatos, N.E. Chakov, George Christou, Stephen Hill,

Porphyrin and Phthalocyanine Chemistry

High-frequency electron paramagnetic resonance (HFEPR) and alternating current (ac) susceptibility measurements are reported for a new high-symmetry ${\text{Mn}}_{12}$ complex, $[{\text{Mn}}_{12}{\text{O}}_{12}{({\text{O}}_{2}{\text{CCH}}_{3})}_{16}{({\text{CH}}_{3}\text{OH})}_{4}]\ensuremath{\cdot}{\text{CH}}_{3}\text{OH}$. The results are compared to those of other high-symmetry spin $S=10\text{ }{\text{Mn}}_{12}$ single-molecule magnets (SMMs), including the original acetate, $[{\text{Mn}}_{12}{({\text{O}}_{2}{\text{CCH}}_{3})}_{16}{({\text{H}}_{2}\text{O})}_{4}]\ensuremath{\cdot}2{\text{CH}}_{3}{\text{CO}}_{2}\text{H}\ensuremath{\cdot}4{\text{H}}_{2}\text{O}$, and the $[{\text{Mn}}_{12}{\text{O}}_{12}{({\text{O}}_{2}{\text{CCH}}_{2}\text{Br})}_{16}{({\text{H}}_{2}\text{O})}_{4}]\ensuremath{\cdot}4{\text{CH}}_{2}{\text{Cl}}_{2}$ and $[{\text{Mn}}_{12}{\text{O}}_{12}{({\text{O}}_{2}{\text{CCH}}_{2}{\text{Bu}}^{t})}_{16}{({\text{CH}}_{3}\text{OH})}_{4}]\ensuremath{\cdot}{\text{CH}}_{3}\text{OH}$ complexes. These comparisons reveal important insights into the factors that influence the values of the effective barrier to magnetization reversal, ${U}_{eff}$, deduced on the basis of ac susceptibility measurements. In particular, we find that variations in ${U}_{eff}$ can be correlated with the degree of disorder in a crystal which can be controlled by desolvating (drying) samples. This highlights the importance of careful sample handling when making measurements on SMM crystals containing volatile lattice solvents. The HFEPR data additionally provide spectroscopic evidence suggesting that the relatively weak disorder induced by desolvation influences the quantum tunneling interactions and that it is under-barrier tunneling that is responsible for a consistent reduction in ${U}_{eff}$ that is found upon drying samples. Meanwhile, the axial anisotropy deduced from HFEPR is found to be virtually identical for all four ${\text{Mn}}_{12}$ complexes, with no measurable reduction upon desolvation.