Lanthanide compounds show much higher energy barriers to magnetic relaxation than 3d-block compounds, and this has led to speculation that they could be used in molecular spintronic devices. Prototype molecular spin valves and molecular transistors have been reported, with remarkable experiments showing the influence of nuclear hyperfine coupling on transport properties. Modelling magnetic data measured on lanthanides is always complicated due to the strong spin-orbit coupling and subtle crystal field effects observed for the 4f-ions; this problem becomes still more challenging when interactions between lanthanide ions are also important. Such interactions have been shown to hinder and enhance magnetic relaxation in different examples, hence understanding their nature is vital. Here we are able to measure directly the interaction between two dysprosium(III) ions through multi-frequency electron paramagnetic resonance spectroscopy and other techniques, and explain how this influences the dynamic magnetic behaviour of the system.
The redox-controlled driven oscillatory template exchange between phosphate (P) and vanadate (V) anions enclosed in an {X 2 M 18 } cluster is reported. Extensive investigations using a range of techniques, including correlated ESI-MS, EPR, and UV−vis as a function of reaction time, showed that six complete oscillations interconverting the capsule species present in solution from {P 2 M 18 } to {V 2 M 18 } were possible, provided that a sufficient concentration of the TEA reducing agent was present in solution.
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