Dinuclear, tetrakis(acetato)-bridged lanthanide(III) complexes from the use of 2-acetylpyridine hydrazone

Anastasiadis, Nikolaos C.; Mylonas-Margaritis, Ioannis; Psycharis, Vassilis; Raptopoulou, Catherine P.; Kalofolias, Dimitris A.; Milios, Constantinos J.; Klouras, N.; Perlepes, Spyros P.

doi:10.1016/j.inoche.2014.11.004

Cited by 13 publications

(13 citation statements)

References 17 publications

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“…Both IR spectra of the two complexes reveal bands which are assigned respectively to asymmetric n as (COO) and symmetric n s (COO) stretching vibrations of the acetate group 28 in the ranges 1565-1550 and 1450-1440 cm -1 . The positions of these asymmetric and symmetric bands are very close proximity in the two spectra of the complexes indicating that the coordination modes of the different acetate groups are similar in all these compounds.…”

Section: General Studiesmentioning

confidence: 99%

Lanthanide(III) complexes with tridentate Schiff base ligand, antioxidant activity and X-ray crystal structures of the Nd(III) and Sm(III) complexes

Gueye¹,

Dieng²,

Thiam³

et al. 2017

S.Afr.j.chem.

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The tridentate N 4 -type Schiff base was synthesized from the condensation reaction of 2-hydrazinopyridine and pyridine-2-carbaldehyde. Neodymium and Samarium complexes were isolated when the corresponding nitrate salt was added to the solution of the ligand. The isolated compounds were characterized by elemental analyses, IR study, room temperature magnetic measurements and single X-ray crystal diffraction of the two crystals. Both complexes crystallize in the monoclinic system with space group P21/c. KEYWORDSLanthanide complexes, hydrazino, antioxidant activity, X-ray structure.

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Section: General Studiesmentioning

confidence: 99%

Lanthanide(III) complexes with tridentate Schiff base ligand, antioxidant activity and X-ray crystal structures of the Nd(III) and Sm(III) complexes

Gueye¹,

Dieng²,

Thiam³

et al. 2017

S.Afr.j.chem.

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“…Our groups have a long-standing, intense interest in the chemistry, magnetism, and photoluminescence of 4f-metal complexes [50][51][52][53][54][55][56] and recently our attention has focused on mononuclear emissive Ln(III) complexes exhibiting slow magnetization relaxation [57]. Our design synthetic strategy is to use ligands that act as terminal (either monodentate or chelating) and possess chromophores that can facilitate efficient energy transfer from their triplet state to the Ln III ions' excited (i.e., emissive) levels.…”

Section: Introductionmentioning

confidence: 99%

Mononuclear Lanthanide(III)-Salicylideneaniline Complexes: Synthetic, Structural, Spectroscopic, and Magnetic Studies

et al. 2018

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The reactions of hydrated lanthanide(III) [Ln(III)] nitrates and salicylideneaniline (salanH) have provided access to two families of mononuclear complexes depending on the reaction solvent used. In MeCN, the products are [Ln(NO3)3(salanH)2(H2O)]·MeCN, and, in MeOH, the products are [Ln(NO3)3(salanH)2(MeOH)]·(salanH). The complexes within each family are proven to be isomorphous. The structures of complexes [Ln(NO3)3(salanH)2(H2O)]·MeCN (Ln = Eu, 4·MeCN_Eu, Ln = Dy, 7·MeCN_Dy; Ln = Yb, 10·MeCN_Yb) and [Ln(NO3)3(salanH)2(MeOH)]·(salanH) (Ln = Tb, 17_Tb; Ln = Dy, 18_Dy) have been solved by single-crystal X-ray crystallography. In the five complexes, the LnIII center is bound to six oxygen atoms from the three bidentate chelating nitrato groups, two oxygen atoms from the two monodentate zwitterionic salanH ligands, and one oxygen atom from the coordinated H2O or MeOH group. The salanH ligands are mutually “cis” in 4·MeCN_Eu, 7·MeCN_Dy and 10·MeCN_Yb while they are “trans” in 17_Tb and 18_Dy. The lattice salanH molecule in 17_Tb and 18_Dy is also in its zwitterionic form with the acidic H atom being clearly located on the imine nitrogen atom. The coordination polyhedra defined by the nine oxygen donor atoms can be described as spherical tricapped trigonal prisms in 4·MeCN_Eu, 7·MeCN_Dy, and 10·MeCN_Yb and as spherical capped square antiprisms in 17_Tb and 18_Dy. Various intermolecular interactions build the crystal structures, which are completely different in the members of the two families. Solid-state IR data of the complexes are discussed in terms of their structural features. 1H NMR data for the diamagnetic Y(III) complexes provide strong evidence that the compounds decompose in DMSO by releasing the coordinated salanH ligands. The solid complexes emit green light upon excitation at 360 nm (room temperature) or 405 nm (room temperature). The emission is ligand-based. The solid Pr(III), Nd(III), Sm(III), Er(III), and Yb(III) complexes of both families exhibit LnIII-centered emission in the near-IR region of the electromagnetic spectrum, but there is probably no efficient salanH→LnIII energy transfer responsible for this emission. Detailed magnetic studies reveal that complexes 7·MeCN_Dy, 17_Tb and 18_Dy show field-induced slow magnetic relaxation while complex [Tb(NO3)3(salanH)2(H2O)]·MeCN (6·MeCN_Tb) does not display such properties. The values of the effective energy barrier for magnetization reversal are 13.1 cm−1 for 7·MeCN_Dy, 14.8 cm−1 for 17_Tb, and 31.0 cm−1 for 18_Dy. The enhanced/improved properties of 17_Tb and 18_Dy, compared to those of 6_Tb and 7_Dy, have been correlated with the different supramolecular structural features of the two families. The molecules [Ln(NO3)3(salanH)2(MeOH)] of complexes 17_Tb and 18_Dy are by far better isolated (allowing for better slow magnetic relaxation properties) than the molecules [Ln(NO3)3(salanH)2(H2O)] in 6·MeCN_Tb and 7·MeCN_Dy. The perspectives of the present initial studies in the Ln(III)/salanH chemistry are discussed.

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“…bpy, phen, terpy, etc.) neutral capping organic ligands, which terminate oligomerization or polymerization by blocking two or three coordination sites per Ln III center [23]. Another method is the simultaneous employment of capping bidentate nitrato groups (nitrato ligands have little tendency for bridging in Ln III chemistry) and neutral or anionic organic ligands that can, in principle, bridge only two metal centers; in addition to the bridging functionality, the ligands should preferably possess "chelating" parts to satisfy the demand for high coordination numbers at the Ln III centers [24][25][26].…”

Section: Introductionmentioning

confidence: 99%

“…Thus, the choice of the primary organic ligands is crucial for the synthesis of Ln III 2 complexes. With all the above in mind and given the recently initiated interest of our groups in Ln III 2 complexes with interesting magnetic and/or luminescence properties [23,[25][26][27], we report here the synthesis, structures and magnetic properties of new such complexes bearing the monoanion of tris(2-hydroxyethyl)amine (the empirical name is triethanolamine, abbreviated hereafter as teaH3, Scheme 1). This ligand is very popular in 3d-and mixed 3d/4f-metal cluster chemistry (representative 3d/4f-metal compounds based on anionic forms of teaH3 are described in refs [28][29][30][31]), but with limited used in homometallic Ln III [37][38][39].…”

Section: Introductionmentioning

confidence: 99%

Using the Singly Deprotonated Triethanolamine to Prepare Dinuclear Lanthanide(III) Complexes: Synthesis, Structural Characterization and Magnetic Studies

et al. 2017

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Abstract:The 1:1 reactions between hydrated lanthanide(III) nitrates and triethanolamine (teaH 3 ) in MeOH, in the absence of external bases, have provided access to the dinuclear complexes [Ln 2 (NO 3 ) 4 (teaH 2 ) 2 ] (Ln = Pr, 1; Ln = Gd, 2; Ln = Tb, 3; Ln = Dy, 4; Ln = Ho, 5) containing the singly deprotonated form of the ligand. Use of excess of the ligand in the same solvent gives mononuclear complexes containing the neutral ligand and the representative compound [Pr(NO 3 )(teaH 3 ) 2 ](NO 3 ) 2 (6) was characterized. The structures of the isomorphous complexes 1·2MeOH, 2·2MeOH and 4·2MeOH were solved by single-crystal X-ray crystallography; the other two dinuclear complexes are proposed to be isostructural with 1, 2 and 4 based on elemental analyses, IR spectra and powder XRD patterns. The IR spectra of 1-6 are discussed in terms of structural features of the complexes. The two Ln III atoms in centrosymmetric 1·2MeOH, 2·2MeOH and 4·2MeOH are doubly bridged by the deprotonated oxygen atoms of the two η 1 :η 1 :η 1 :η 2 :µ 2 teaH 2 − ligands. The teaH 2 − nitrogen atom and six terminal oxygen atoms (two from the neutral hydroxyl groups of teaH 2 − and four from two slightly anisobidentate chelating nitrato groups) complete 9-coordination at each 4f-metal center. The coordination geometries of the metal ions are spherical-relaxed capped cubic (1·2MeOH), Johnson tricapped trigonal prismatic (2·2MeOH) and spherical capped square antiprismatic (4·2MeOH). O-H···O H bonds create chains parallel to the a axis. The cation of 6 has crystallographic two fold symmetry and the rotation axis passes through the Pr III atom, the nitrogen atom of the coordinated nitrato group and the non-coordinated oxygen atom of the nitrato ligand. The metal ion is bound to the two η 1 :η 1 :η 1 :η 1 teaH 3 ligands and to one bidentate chelating nitrato group. The 10-coordinate Pr III atom has a sphenocoronal coordination geometry. Several H bonds are responsible for the formation of a 3D architecture in the crystal structure of 6. Complexes 1-6 are new members of a small family of homometallic Ln III complexes containing various forms of triethanolamine as ligands. Dc magnetic susceptibility studies in the 2-300 K range reveal the presence of a weak to moderate intramolecular antiferromagnetic exchange interaction (J = −0.30(2) cm −1 based on the spin HamiltonianĤ = −J(Ŝ Gd1 ·Ŝ Gd1 )) for 2 and probably weak antiferromagnetic exchange interactions within the molecules of 3-5. The antiferromagnetic Gd III ···Gd III interaction in 2 is discussed in terms of known magnetostructural correlations for complexes possessing the {Gd 2 (µ 2 -OR) 2 } 4+ core. Ac magnetic susceptibility measurements in zero dc field for 3-5 do not show frequency dependent out-of-phase signals; this experimental fact is discussed and rationalized for complex 4 in terms of the magnetic anisotropy axis for each Dy III center and the oblate electron density of the metal ion.

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Dinuclear, tetrakis(acetato)-bridged lanthanide(III) complexes from the use of 2-acetylpyridine hydrazone

Cited by 13 publications

References 17 publications

Lanthanide(III) complexes with tridentate Schiff base ligand, antioxidant activity and X-ray crystal structures of the Nd(III) and Sm(III) complexes

Lanthanide(III) complexes with tridentate Schiff base ligand, antioxidant activity and X-ray crystal structures of the Nd(III) and Sm(III) complexes

Mononuclear Lanthanide(III)-Salicylideneaniline Complexes: Synthetic, Structural, Spectroscopic, and Magnetic Studies

Using the Singly Deprotonated Triethanolamine to Prepare Dinuclear Lanthanide(III) Complexes: Synthesis, Structural Characterization and Magnetic Studies

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