Binuclear CuLn complexes (LnIII= Gd, Tb, Dy) of alcohol-functionalized bicompartmental Schiff-base ligand. Hydrogen bonding and magnetic behaviors

Fellah, Fatima Zohra Chiboub; Boulefred, Soumia; Fellah, Abdelghani Chiboub; Rez, Bahjat El; Duhayon, Carine; Sutter, Jean‐Pascal

doi:10.1016/j.ica.2015.09.032

Cited by 18 publications

(4 citation statements)

References 43 publications

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“…Understanding the mechanism of the exchange interaction between the 3d-ion and 4f-ion is important in many different research areas. Indeed, it modulates the magnetic properties of bulk systems such as spinels, orthoferrites, garnets, magneto-optical devices, permanent magnets (such as Sm 5 Co and Nd 2 Fe 14 B), high-temperature superconducting materials (YBa 2 Cu 3 O 7– x ), and so forth. − Insights of its behavior in 0-dimensional 3d–4f complexes are also a cutting-edge research area currently. − …”

Section: Introductionmentioning

confidence: 99%

Probing the Origin of Ferro-/Antiferromagnetic Exchange Interactions in Cu(II)–4f Complexes

et al. 2022

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The mechanistic investigations between Cu(II) and the anisotropic lanthanides (Ln(III)) are not much explored to date. This is due to the complicated energy spectrum which arises due to the orbital angular momentum of anisotropic lanthanides. Interestingly, the exchange coupling J in Ln(III)−Cu(II) systems was found to be antiferromagnetic for <4f 7 metal ions and ferromagnetic for ≥4f 7 metal ions, while the net magnitude of J Total strength gradually decreases moving from f 1 to f 13 . While this is established in several examples, the reason for this intriguing trend is not rationalized. In this article, we have taken up these challenging tasks by synthesizing a family of complexes with the general molecular formula [Cu 2 Ln(HL) 4 (NO 3 )](NO 3 ) 2 , where Ln = La (1 -La ), Ce (2 -Ce ), Pr (3 -Pr ), Gd (4 -Gd ), Tb (5 -Tb ), Dy (6 -Dy ), and Ho (7 -Ho ) and HL = C 15 H 15 N 1 O 3 ; (2methoxy-6-[(E)-2′-hydroxymethyl-phenyliminomethyl]-phenolate) is a monodeprotonated tridentate Schiff base ligand. Detailed dc magnetic susceptibility measurements performed for all the complexes reveal that the Cu(II) ion is coupled ferromagnetically to the respective Ln(III) ion, which has more than seven electrons in the 4f shell, while an antiferromagnetic coupling is witnessed if Ln(III) has less than seven electrons. The strength of the exchange coupling constant was quantitatively determined for representative complexes from the high-field/high-frequency electron paramagnetic resonance spectroscopy which follows the order of 4 -Gd (1.50(10) cm −1 ) > 5 -Tb (1.18(10) cm −1 ) > 6 -Dy (0.56(10) cm −1 based on the −

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Section: Introductionmentioning

confidence: 99%

Probing the Origin of Ferro-/Antiferromagnetic Exchange Interactions in Cu(II)–4f Complexes

et al. 2022

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“…32) where H 2 L1 = 1,3-bis(2-hydroxy-3-methoxybenzylidene)propan-2-ol. 80 Of these complexes, only (30) displayed SMM properties with an U eff barrier of 24.6 K. In all complexes, the alcohol group acts as a hydrogen bond donor for intermolecular interactions and a hydrogen bond acceptor for intramolecular interactions (Fig. 7).…”

Section: Changing Electron Densitymentioning

confidence: 99%

“…Fellah et al investigated the effects a non-coordinating alcohol group had on the magnetic properties of a series of four binuclear CuLn complexes, [Cu L1 (H 2 O)Gd(NO 3 ) 2 (H 2 O) 2 ]·NO 3 ( 29 ), [Cu L1 (MeOH)Tb(NO 3 ) 3 ] ( 30 ), [Cu L1 (MeOH)Dy(NO 3 ) 3 ] ( 31 ), and [Cu L1 (H 2 O)Dy(NO 3 ) 3 ] ( 32 ) where H 2 L1 = 1,3-bis(2-hydroxy-3-methoxybenzylidene)propan-2-ol. 80 Of these complexes, only ( 30 ) displayed SMM properties with an U eff barrier of 24.6 K. In all complexes, the alcohol group acts as a hydrogen bond donor for intermolecular interactions and a hydrogen bond acceptor for intramolecular interactions (Fig. 7).…”

Section: Positive Effectsmentioning

confidence: 99%

The importance of second sphere interactions on single molecule magnet performance

Matheson,

Dais,

Donaldson

et al. 2023

Inorg. Chem. Front.

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“…The ligand molecules with 1,3-diamino-2-propanol bridge may undergo double or triple deprotonation forming N 2 O 2 or N 2 O 3 coordination pockets ( Table S1 ). The doubly deprotonated ligands form classic mono- up to tetranuclear coordination compounds [ 11 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 ]. But only the triple deprotonation enables the higher nuclearity of complexes: to hexa- [ 22 , 30 ] and heptanuclear units [ 31 ] with the use of additional anions such as nitrate or acetate.…”

Section: Introductionmentioning

confidence: 99%

Heterometallic ZnII–LnIII–ZnII Schiff Base Complexes with Linear or Bent Conformation—Synthesis, Crystal Structures, Luminescent and Magnetic Characterization

2018

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A series of racemic, heteronuclear complexes [Zn2Nd(ac)2(HL)2]NO3·3H2O (1), [Zn2Sm(ac)2(HL)2]NO3·3CH3OH·0.3H2O (2), [Zn2Ln(ac)2(HL)2]NO3·5.33H2O (3–5) (where HL is the dideprotonated form of N,N′-bis(5-bromo-3-methoxysalicylidene)-1,3-diamino-2-propanol, ac = acetate ion, and Ln = Eu (3), Tb (4), Dy (5), respectively) with an achiral multisite coordination Schiff base ligand (H3L) were synthesized and characterized. The X-ray crystallography revealed that the chirality in complexes is centered at lanthanide(III) ions due to two vicinally located μ-acetato-bridging ligands. The presented crystals have isoskeletal coordination units but they crystallize in monoclinic (1, 2) or trigonal crystal systems (3–5) with slightly different conformation. In 1 and 2 the ZnII–LnIII–ZnII coordination core is linear, whereas in isostructural crystals 3–5 the chiral coordination cores are bent and lie on a two-fold axis. The complexes 1, 3–5 show a blue emission attributed to the emission of the ligand. For ZnII2SmIII complex (2) the characteristic emission bands of f-f* transitions were observed. The magnetic properties for compounds 1, 4 and 5 are characteristic for the paramagnetism of the corresponding lanthanide(III) ions.

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Binuclear CuLn complexes (LnIII= Gd, Tb, Dy) of alcohol-functionalized bicompartmental Schiff-base ligand. Hydrogen bonding and magnetic behaviors

Cited by 18 publications

References 43 publications

Probing the Origin of Ferro-/Antiferromagnetic Exchange Interactions in Cu(II)–4f Complexes

Probing the Origin of Ferro-/Antiferromagnetic Exchange Interactions in Cu(II)–4f Complexes

The importance of second sphere interactions on single molecule magnet performance

Heterometallic ZnII–LnIII–ZnII Schiff Base Complexes with Linear or Bent Conformation—Synthesis, Crystal Structures, Luminescent and Magnetic Characterization

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