NDLI: Enhancement of $Tb^{III}–Cu^{II}$ Single‐Molecule Magnet Performance through Structural Modification

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Enhancement of $Tb^{III}–Cu^{II}$ Single‐Molecule Magnet Performance through Structural Modification

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Heras Ojea, María José Wernsdorfer, Wolfgang Milway, Victoria A. Wilson, Claire Murrie, Mark Velmurugan, Gunasekaran Thomas, Lynne H. Coles, Simon J. Rajaraman, Gopalan
Description	Author Affiliation: 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.)
Abstract	We report a series of 3d–4f complexes $\{Ln_{2}Cu_{3}(H_{3}L)_{2}X_{n}\}$ $(X=OAc^{−},$ Ln=Gd, Tb or $X=NO_{3}$ $^{−},$ Ln=Gd, Tb, Dy, Ho, Er) using the 2,2′‐(propane‐1,3‐diyldiimino)bis[2‐(hydroxylmethyl)propane‐1,3‐diol] $(H_{6}L)$ 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 $\{Tb_{2}Cu_{3}(H_{3}L)_{2}X_{n}\}$ complexes is seen by changing the auxiliary ligands $(X=OAc^{−}$ for $NO_{3}$ $^{−}).$ 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 (C $_{4v}$ versus $C_{s}).$
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	36
Volume Number	22
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2016-08-26
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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