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Updated: Jun 7, 2025
Controlling the Size, Shape and Stability of Supramolecular Polymers in Water
Published on: August 2, 2012
Influence of weakly coordinating anions binding to the hexa-tert-butyl dysprosocenium cation
Sophie C Corner1, Gemma K Gransbury1, David P Mills1
1Department of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK. david.mills@manchester.ac.uk.
Abstract:
Complexes containing isolated dysprosocenium cations, [Dy(CpR)2][WCA] (CpR = substituted cyclopentadienyl, WCA = weakly coordinating anion), have recently emerged as leading examples of high-temperature single-molecule magnets (SMMs) due to a combination of the axial orientation and rigidity of the CpR rings. However, our understanding of the effects of transverse fields on the magnetic properties of [Dy(CpR)2]+ cations is underdeveloped. Here we investigate the impact of equatorially-bound WCAs via the synthesis of the Dy(III) bis-CpR complexes [Dy(Cpttt)2{AlCl[OC(CF3)3]3-κ-Cl}] (1) and [Dy(Cpttt)2{AlCl(C2H5)[OC(C6F5)3]2-κ-Cl}] (2), and their characterisation by single crystal XRD, elemental analysis, ATR-IR and NMR spectroscopy, and ab initio calculations. Despite the similarity of the Dy coordination spheres in 1 and 2 we find that their effective energy barriers to reversal of magnetisation are vastly different (Ueff = 886(17) cm-1 and 559(18) cm-1, respectively) and they both show waist-restricted magnetic hysteresis at 2 K. Together, these data provide fresh insights into the sensitivity of the magnetic properties of [Dy(CpR)2]+ cations to relatively weak equatorial interactions.
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