Dedicated to Professor Dante Gatteschi on the occasion of his 60th birthdayThe study of paramagnetic metal-ion aggregates has been of increasing interest since the observation that such molecules can exhibit magnetic memory effects. [1][2][3] Termed singlemolecule magnets or SMMs, the important factors leading to such properties derive from the combination of a large ground-state spin and a large magnetic anisotropy of the Ising (easy-axis) type. Studies have largely been based on transition-metal compounds since they typically exhibit both of the aforementioned features. The incorporation of lanthanides into these complexes has been investigated to take advantage of the potentially large number of unpaired f-electrons available. [4][5][6][7] However, very little work has been done to date on purely lanthanide-based systems. [8,9] The origin of SMM behavior in lanthanide-containing compounds is more complicated than that of d-block transition-metal ions since there is likely to be a significant orbital component. In the lanthanide-containing phthalocyanine complexes reported in the literature the ligand environment induces a large splitting of the ground J manifold, whereas in SMMs large-spin ground states arising from magnetic interactions between the metal centers of the cluster can enhance the weaker single-ion
Dedicated to Professor Hansgeorg Schnöckel on the occasion of his 65th birthday.The first evidence of single molecule magnet (SMM) behavior was discovered in the mixed-valence compounds [Mn [1] In the quest to synthesize SMMs that show hysteresis at higher temperatures, it has been recognized that large ground-state spins and a uniaxial anisotropy (large negative D and small E considering the following Hamiltonian anisotropy term:It is thus of interest to discover how to obtain the largest-spin ground state possible for a given size of aggregate. As well as having four unpaired electrons in its high-spin state, the Mn III ion is particularly useful for introducing large anisotropies through the presence of Jahn-Teller distortions in this configuration and has been the most thoroughly studied candidate for synthesizing new SMMs. Amongst the large number of aggregates containing manganese(III) in the literature, a Mn 25 cluster has been reported as having a ground spin state of 51/2.[4] Herein we report on the realization of the maximum-spin ground state of 83/2 for the aggregate [Mn
Separate areas of differing polarity in the structure of an inorganic cluster compound are favored by the introduction of organic ligands on the periphery of the aggregate. This has been demonstrated by the synthesis of compounds containing the title anion (see picture for an example).
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