Enhancement of TbIII–CuII Single‐Molecule Magnet Performance through Structural Modification |
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| Authors: | María José Heras?Ojea Dr Victoria A Milway Dr Gunasekaran Velmurugan Dr Lynne H Thomas Dr Simon J Coles Dr Claire Wilson Dr Wolfgang Wernsdorfer Prof Gopalan Rajaraman Dr Mark Murrie |
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| Institution: | 1. WestCHEM, School of Chemistry, University of Glasgow, Glasgow, UK;2. Department of Chemistry, Indian Institute of Technology Bombay, Mumbai, Maharashtra, India;3. Department of Chemistry, University of Bath, Bath, UK;4. Department of Chemistry, University of Southampton, Southampton, UK;5. CNRS, Inst NEEL & Univ. Grenoble Alpes, Grenoble, France |
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| Abstract: | We report a series of 3d–4f complexes {Ln2Cu3(H3L)2Xn} (X=OAc?, Ln=Gd, Tb or X=NO3?, Ln=Gd, Tb, Dy, Ho, Er) using the 2,2′‐(propane‐1,3‐diyldiimino)bis2‐(hydroxylmethyl)propane‐1,3‐diol] (H6L) pro‐ligand. All complexes, except that in which Ln=Gd, show slow magnetic relaxation in zero applied dc field. A remarkable improvement of the energy barrier to reorientation of the magnetisation in the {Tb2Cu3(H3L)2Xn} complexes is seen by changing the auxiliary ligands (X=OAc? for NO3?). This leads to the largest reported relaxation barrier in zero applied dc field for a Tb/Cu‐based single‐molecule magnet. Ab initio CASSCF calculations performed on mononuclear TbIII models are employed to understand the increase in energy barrier and the calculations suggest that the difference stems from a change in the TbIII coordination environment (C4v versus Cs). |
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| Keywords: | copper heterometallic complexes lanthanides magnetic properties single-molecule magnets |
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