Enhancement of Tb(III) -Cu(II) Single-Molecule Magnet Performance through Structural Modification.
| Autor: | Heras Ojea MJ; WestCHEM, School of Chemistry, University of Glasgow, University Avenue, Glasgow, G12 8QQ, UK., Milway VA; WestCHEM, School of Chemistry, University of Glasgow, University Avenue, Glasgow, G12 8QQ, UK., Velmurugan G; Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, Maharashtra, 400 076, India., Thomas LH; Department of Chemistry, University of Bath, Bath, BA2 7AY, UK., Coles SJ; Department of Chemistry, University of Southampton, Southampton, SO17 1BJ, UK., Wilson C; WestCHEM, School of Chemistry, University of Glasgow, University Avenue, Glasgow, G12 8QQ, UK., Wernsdorfer W; CNRS, Inst NEEL & Univ. Grenoble Alpes, 38000, Grenoble, France., Rajaraman G; Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, Maharashtra, 400 076, India. rajaraman@chem.iitb.ac.in., Murrie M; WestCHEM, School of Chemistry, University of Glasgow, University Avenue, Glasgow, G12 8QQ, UK. Mark.Murrie@glasgow.ac.uk. |
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| Jazyk: | angličtina |
| Zdroj: | Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2016 Aug 26; Vol. 22 (36), pp. 12839-48. Date of Electronic Publication: 2016 Aug 03. |
| DOI: | 10.1002/chem.201601971 |
| Abstrakt: | We report a series of 3d-4f complexes {Ln2 Cu3 (H3 L)2 Xn } (X=OAc(-) , Ln=Gd, Tb or X=NO3 (-) , Ln=Gd, Tb, Dy, Ho, Er) using the 2,2'-(propane-1,3-diyldiimino)bis[2-(hydroxylmethyl)propane-1,3-diol] (H6 L) 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 {Tb2 Cu3 (H3 L)2 Xn } 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 Tb(III) models are employed to understand the increase in energy barrier and the calculations suggest that the difference stems from a change in the Tb(III) coordination environment (C4v versus Cs ). (© 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.) |
| Databáze: | MEDLINE |
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