Homoscorpionates (hydridotris(1-pyrazolyl)borato complexes) of the trivalent 4fions. The crystal and molecular structure of [(HB(N2C3H3)3]3LnIII, (Ln  Pr, Nd)

Apostolidis, Christos; Rébizant, J.; Kanellakopulos, Β.; Ammon, R. von; Dornberger, E.; Müller, Jan; Powietzka, B.; Nuber, Bernhard

doi:10.1016/s0277-5387(96)00391-9

Cited by 52 publications

(56 citation statements)

References 21 publications

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“…This result is a promising indication that the Cl 2 CA 2− ligand in 3 is in the o-quinone form [28]. Furthermore, the presence of the ancillary Tp -ligands in 1-3 is confirmed by characteristic absorptions in their IR spectra at approximately 2470 cm −1 (c.f., KTp − , νB-H =~2440 cm −1 ) [29]. …”

Section: Syntheses and Characterizationsmentioning

confidence: 97%

Field-Induced Slow Magnetic Relaxation of Mono- and Dinuclear Dysprosium(III) Complexes Coordinated by a Chloranilate with Different Resonance Forms

et al. 2017

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Abstract:We synthesized the dinuclear and mononuclear dysprosium(III) complexes [{Dy(Tp) 2 } 2 (Cl 2 An)]·2CH 2 Cl 2 (1) and [Co(Cp) 2 ][Dy(Tp) 2 (Cl 2 An)] (3), where Cl 2 An 2− and Tp − are the chloranilate and hydrotris(pyrazolyl)borate ligand, respectively. In addition, the magnitude of the magnetic coupling between the lanthanide centers through the Cl 2 An 2− bridge has been probed through the synthesis of [{Gd(Tp) 2 } 2 (Cl 2 An)]·2CH 2 Cl 2 (2), which is a gadolinium(III) analogue of 1. Complexes 1-3 were characterized by infrared (IR) spectroscopy, elemental analysis, single-crystal X-ray diffraction, and SQUID measurements. IR and single-crystal X-ray structural analyses confirm that the coordination environments of the lanthanide(III) centers in 1 and 3 are similar to each other; i.e., eight-coordinated metal centers, each occupied by an N 6 O 2 donor set from two Tp − ligands and one Cl 2 An 2− ligand. The coordination geometries of the lanthanide(III) centers in 1 and 2 are distorted triangular dodecahedral, while that in the mononuclear complex 3 is square antiprismatic, where the Cl 2 An 2− ligand takes the bi-separated delocalized form in 1 and 2, and the o-quinone form in 3. Alternating-current (AC) magnetic studies clearly reveal that both 1 and 3 exhibit field-induced slow relaxations of magnetization that occur via Raman and direct processes. Complexes 1 and 3 exhibit different spin relaxation behavior, which reflects the coordination geometry around each Dy III center and its nuclearity, as well as the molecular packing in the crystal lattice. Although the magnetic analysis of 2 revealed negligible magnetic coupling, Cl 2 An 2− bridges with small biases may form in the dinuclear complexes, which play roles in the spin relaxation dynamics through dipolar interactions.

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Section: Syntheses and Characterizationsmentioning

confidence: 97%

Field-Induced Slow Magnetic Relaxation of Mono- and Dinuclear Dysprosium(III) Complexes Coordinated by a Chloranilate with Different Resonance Forms

et al. 2017

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“…[54] For this reason, it was originally assumed that this also holds for homoleptic nine-coordinate [Ln(η 3 -Tp) 3 ] (Ln ϭ LaϪTb) [55,56] and [Ln(COT)(η 3 -Tp Me 2)] (Ln ϭ Pr, Nd, Sm), [16Ϫ19] where the N atoms of the Tp Me 2 ligands have only somewhat shorter distances from the Ln central ions [57] as in [Ln(Tp) 3 ]. [55,56] Thus, we neglected the contribution of the Tp In order to examine the above assumption of a low CF strength of the Tp Me 2 or Tp ligand, we recently analyzed the optical spectra of homoleptic [Ln(η 3 -Tp) 3 ] (Ln ϭ Eu, Pr) [56,58] and found averaged CF strengths of 149 cm Ϫ1 [56] and 194 cm Ϫ1 , [58] By means of compound 1 and applying method A, the individual CF strength of the C 5 H 4 tBu Ϫ ligand was estimated to be 583 cm Ϫ1 (vide supra). This value is approximately three times greater than that of the Tp ligand and thus the contribution of the η 3 -and η 2 -coordinated Tp Me 2 ligands to the global CF strength of complex 1 cannot be neglected.…”

Section: Cf Analysesmentioning

confidence: 99%

Crystal Field Strengths, Nephelauxetic Effects, and Experimentally Based Molecular Orbital Schemes (in the f Range) of Selected Cyclopentadienyl Complexes of Samarium(III)

et al. 2003

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The absorption and luminescence spectra of pseudo (ψ) trigonal planar [Sm(η5‐C5H4tBu)3] (1), low symmetric [Sm(η5‐Cp)(η3‐Tp)(η2‐Tp)] (Cp = η5‐cyclopentadienyl; Tp = hydrotris(3,5‐dimethylpyrazolyl)borato) (2) as well as ψ trigonal pyramidal [Sm(η5‐C5H4tBu)3(THF)] (3), [Sm(η5‐Cp)3(THF)] (4) and [Sm(η5‐Cp)3(CNC6H11)] (5) have been measured at room and low temperatures. From the spectra obtained, truncated crystal field (CF) splitting patterns of these compounds could be derived, and simulated by fitting the parameters of a phenomenological Hamiltonian. On the basis of the CF parameters used, the global CF strengths experienced by the Sm3+ central ions of complexes 1−5, as well as the individual CF strength associated with one C5H4tBu− ligand are estimated. The obtained Slater parameters F2 and the spin‐orbit coupling parameters ζ4f allow the insertion of compounds 1−5 into truncated nephelauxetic and relativistic nephelauxetic series. Besides, the experimentally based non‐relativistic and relativistic molecular orbital schemes (in the f range) of complexes 1 and, partly, 3 are set up and compared with the results of quantum chemical model calculations. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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“…Previous studies on tris(dihydrobispyrazolylborato)yttrium-(III) 40 [Y(Bpz) 3 ] and on tris(hydrotrispyrazolylborato)-neodymium(III) and its praseodymium(III) analogue 41 [Ln-(Tpz) 3 ] have shown that the coordination sphere around the metal center was a tricapped trigonal regular prism. It has been demonstrated by 89 Y NMR that there exist B−H···Y agostic bonds in [Y(Bpz) 3 ], allowing a 9-coordinated geometry.…”

Section: ■ Introductionmentioning

confidence: 99%

New Family of Lanthanide-Based Complexes with Different Scorpionate-Type Ligands: A Rare Case Where Dysprosium and Ytterbium Analogues Display Single-Ion-Magnet Behavior

Lannes

Luneau

2015

Inorg. Chem.

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A new family of lanthanide complexes [Ln(Tpz)2Bpz]·xCH2Cl2 (Ln = Gd, Tb, Dy, Ho, x = 0.5; Ln = Yb, x = 1; Tpz = hydrotris(pyrazolyl)borate; Bpz = dihydrobis(pyrazolyl)borate) has been synthesized. Those complexes have been characterized by single-crystal X-ray diffraction, and the magnetic properties have been investigated. Both dysprosium and ytterbium analogues display single-ion-magnet behavior, despite the difference in their spatial distribution of 4f electronic charges. Theoretical calculations with crystal field parameters have been carried out to gain better insight of the relaxation pathways that may be involved in those two complexes.

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Homoscorpionates (hydridotris(1-pyrazolyl)borato complexes) of the trivalent 4fions. The crystal and molecular structure of [(HB(N2C3H3)3]3LnIII, (Ln  Pr, Nd)

Cited by 52 publications

References 21 publications

Field-Induced Slow Magnetic Relaxation of Mono- and Dinuclear Dysprosium(III) Complexes Coordinated by a Chloranilate with Different Resonance Forms

Field-Induced Slow Magnetic Relaxation of Mono- and Dinuclear Dysprosium(III) Complexes Coordinated by a Chloranilate with Different Resonance Forms

Crystal Field Strengths, Nephelauxetic Effects, and Experimentally Based Molecular Orbital Schemes (in the f Range) of Selected Cyclopentadienyl Complexes of Samarium(III)

New Family of Lanthanide-Based Complexes with Different Scorpionate-Type Ligands: A Rare Case Where Dysprosium and Ytterbium Analogues Display Single-Ion-Magnet Behavior

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