Towards comparative investigation of Er- and Yb-based SMMs: the effect of the coordination environment configuration on the magnetic relaxation in the series of heteroleptic thiocyanate complexes

We prepared and studied two similar series of Er and Yb thiocyanates, involving [Ln(H 2 O) 5 (NCS) 3 ]·H 2 O ( 1Er , 1Yb ) as well as the molecular and ionic complexes with 2,2′-bipyridine (bpy) and 1,10-phenantroline (phen), [Ln(H 2 O)(bpy) 2 (NCS) 3 ]·0.5(bpy)·H 2 O ( 2Er , 2Yb ), [Ln(H 2 O)(phen)...

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Published in:Dalton transactions : an international journal of inorganic chemistry 2019-08, Vol.48 (33), p.12644-12655
Main Authors: Petrosyants, Svetlana P, Babeshkin, Konstantin A, Gavrikov, Andrey V, Ilyukhin, Andrey B, Belova, Ekaterina V, Efimov, Nikolay N
Format: Article
Language:English
Subjects:
Configurations
Crystallography
Data acquisition
Erbium
Magnetic induction
Magnetic properties
Magnetic relaxation
Magnetization reversal
Magnets
Thiocyanates
Ytterbium
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Summary:We prepared and studied two similar series of Er and Yb thiocyanates, involving [Ln(H 2 O) 5 (NCS) 3 ]·H 2 O ( 1Er , 1Yb ) as well as the molecular and ionic complexes with 2,2′-bipyridine (bpy) and 1,10-phenantroline (phen), [Ln(H 2 O)(bpy) 2 (NCS) 3 ]·0.5(bpy)·H 2 O ( 2Er , 2Yb ), [Ln(H 2 O)(phen) 2 (NCS) 3 ]·phen·0.5H 2 O ( 3Er , 3Yb ), [Hbpy][Ln(bpy) 2 (NCS) 4 ]·H 2 O ( 4Er , 4Yb ) and [Hphen][Ln(phen) 2 (NCS) 4 ] ( 5Er , 5Yb ). All the complexes were found to exhibit the properties of field-induced single-molecule magnets. For 1Yb , the effective value of the energy barrier for magnetization reversal, Δ eff / k B , equals to 50 K, which is among the highest ones currently known for molecular SMMs based on Yb 3+ . The obtained data are discussed involving essential structural features of the complexes, namely the configuration of the Ln environment, i.e. its composition and geometry as well as mutual distribution of different donating centers. To the best of our knowledge, this work also involves experimental investigation of the largest and thus sufficiently representative series of similar mononuclear SMMs based on Er and Yb within one study. Two series of Er and Yb thiocyanates were studied as SMMs. Some empirical patterns for further development of Er and Yb based SMMs were proposed. The Δ eff value for Yb aquathiocyanate is among the highest known for molecular complexes of this Ln.
ISSN:1477-9226
1477-9234
DOI:10.1039/c9dt02260k