Exploring Tuning of Structural and Magnetic Properties by Modification of Ancillary β-Diketonate Co-ligands in a Family of Near-Linear Tetranuclear DyIII Complexes

J Acharya, S Biswas, J van Leusen… - Crystal Growth & …, 2018 - ACS Publications
J Acharya, S Biswas, J van Leusen, P Kumar, V Kumar, RS Narayanan, P Kögerler
Crystal Growth & Design, 2018ACS Publications
Three tetranuclear DyIII complexes,[Dy4 (LH) 2 (CH3OH) 4 (acac) 6](1),[Dy4 (LH) 2
(CH3OH) 4 (hmacac) 6]· 2CH3OH (2), and [Dy4 (LH) 2 (CH3OH) 4 (dpacac) 6]· 2CHCl3·
2CH3OH· 2H2O (3), have been synthesized and characterized [LH4=(2 E, N′ E)-N′-(2, 3-
dihydroxybenzylidene)-2-(hydroxyimino) propanehydrazide; acacH= acetylacetone;
hmacacH= 2, 2, 6, 6-tetramethyl-3, 5-heptanedione; dpacacH= dibenzoylmethane]. The
structural elucidation of these complexes reveals two types of DyIII centers in terms of the …
Three tetranuclear DyIII complexes, [Dy4(LH)2(CH3OH)4(acac)6] (1), [Dy4(LH)2(CH3OH)4(hmacac)6]·2CH3OH (2), and [Dy4(LH)2(CH3OH)4(dpacac)6]·2CHCl3·2CH3OH·2H2O (3), have been synthesized and characterized [LH4 = (2E,NE)-N′-(2,3-dihydroxybenzylidene)-2-(hydroxyimino)propanehydrazide; acacH = acetylacetone; hmacacH = 2,2,6,6-tetramethyl-3,5-heptanedione; dpacacH = dibenzoylmethane]. The structural elucidation of these complexes reveals two types of DyIII centers in terms of the number of ancillary β-diketonate co-ligands coordinated to the metal centers. Detailed magnetic studies have been carried out on 13 which reveal a slow relaxation of magnetization at low temperatures. The relaxation of complexes 2 and 3 is distributed in three temperature ranges: lower temperature process, transition range, and higher temperature process. In the higher temperature range, the best fitting of the data for 2 yields τ0 = (6.3 ± 3.6) × 10–6 s and Ueff = (23.8 ± 4.0) K, and for 3, τ0 = (9.4 ± 5.9) × 10–6 s, Ueff = (29.0 ± 6.3) K.
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