Facile Interchange of 3d and 4f Ions in Single‐Molecule Magnets: Stepwise Assembly of [Mn4], [Mn3Ln] and [Mn2Ln2] Cages within Calix[4]arene Scaffolds |
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| Authors: | Dr. Maria A. Palacios Dr. Ross McLellan Dr. Christine M. Beavers Dr. Simon J. Teat Dr. Høgni Weihe Dr. Stergios Piligkos Dr. Scott J. Dalgarno Prof. Euan K. Brechin |
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| Affiliation: | 1. EaStCHEM School of Chemistry, The University of Edinburgh, David Brewster Road, Edinburgh EH9 3FJ (UK);2. Institute of Chemical Sciences, Heriot‐Watt University, Riccarton, Edinburgh, Scotland EH14 4AS (UK);3. Lawrence Berkeley National Laboratory, 1?Cyclotron Road, MS 6R2100, Berkeley, California 94720 (USA);4. Department of Chemistry, University of Copenhagen, Universitetsparken?5, 2100 (Denmark) |
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| Abstract: | The central MnII ions in a series of calix[4]arene‐stabilised butterflies can be sequentially replaced with LnIII ions, maintaining the structural integrity of the molecule but transforming its magnetic properties. The replacement of MnII for GdIII allows for the examination of the transferability of spin‐Hamiltonian parameters within the family as well as permitting their reliable determination. The introduction of the 4f ions results in weaker intramolecular magnetic exchange, an increase in the number of low‐lying excited states, and an increase in magnetisation relaxation, highlighting the importance of exchange over single‐ion anisotropy for the observation of SMM behaviour in this family of complexes. The presence of the [TMII/III(TBC[4])(OH)(solvent)] metalloligand (TM=transition metal, TBC=p‐tBu‐calix[4]arene) suggests that magnetic calix[n]arene building blocks can be employed to encapsulate a range of different “guests” within structurally robust “hosts”. |
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| Keywords: | calixarenes clusters coordination chemistry magnetism SMMs |
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