Tripodal Oxazolidine-N-Oxyl Diradical Complexes of Dy3+ and Eu3+

Rey, P.; Caneschi, Andréa; Sukhikh, Taisiya S.; Vostrikova, Kira E.

doi:10.3390/inorganics9120091

Cited by 8 publications

(11 citation statements)

References 53 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Note that, in the literature, we have not found either free hydroxylamine (RadH) or its complexes. As for the second organic ligand, hbpm , apart from 1 , only two Ln-compounds have been structurally characterized: the binuclear complex, [Eu 2 ( dpk ) 2 ( hbpm ) 2 (CF 3 SO 3 ) 2 ] ( dpk is 2,2′-dipyridyl ketone), which we recently communicated [ 17 ], and one Dy 3+ polynuclear complex [ 30 ]. Unlike the first two compounds, in which the olate O-atom is μ 2 -bridging; in the latter, the same oxygen is μ 3 -coordinated.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Oxazolidine Nitroxide Transformation in a Coordination Sphere of the Ln3+ Ions

2022

Self Cite

View full text Add to dashboard Cite

Upon the interaction of the hydrated lanthanide(III) salts found in acetonitrile solution with a tripodal paramagnetic compound, 4,4-dimethyl-2,2-bis(pyridin-2-yl)-1,3-oxazolidine-3-oxyl (Rad), functionalized by two pyridyl groups, three neutral, structurally characterized complexes with diamagnetic polydentate ligands—[Dy(RadH)(hbpm)Cl2], [Yb2(ipapm)2(NO3)4], and [Ce2(ipapm)2(NO3)4(EtOAc)2]—were obtained. These coordination compounds are minor uncolored crystalline products, which were formed in a reaction mixture due to the Rad transformation in a lanthanide coordination sphere, wherein the processes of its simultaneous disproportionation, hydrolysis, and condensation proceed differently than in the absence of Ln ions. The latter fact was confirmed by the formation of the structurally characterized product of the oxazolidine nitroxide transformation during its crystallization in toluene solution. Such a conversion in the presence of 4f elements ions is unique since no similar phenomenon was observed during the synthesis of the 3d-metal complexes with Rad.

show abstract

Section: Resultsmentioning

confidence: 99%

“…The terbium congener displays frequency-dependent, out-of-phase signals in the zero field, designating single-molecule magnetic behavior. In a just-published communication, the two diradical complexes, [LnRad 2 (CF 3 SO 3 ) 3 ], Ln = Dy and Eu, were reported [ 17 ].…”

Section: Introductionmentioning

confidence: 99%

Oxazolidine Nitroxide Transformation in a Coordination Sphere of the Ln3+ Ions

2022

Self Cite

View full text Add to dashboard Cite

show abstract

“…In both compounds, a europium center has a coordination number of ten consisting of three nitrogens of trispyrazolylmethane, six oxygens of bidentate nitrate anions and one aqua-oxygen, Figure 1. The Eu-N distances of 1 are in the range of 2.5810(12) to 2.5932(12) Å, which are somewhat larger than those for nitrates (2.4846(10)-2.5687(11) Å), the distance of the Eu-Oaqua bond of 2.4191 (11) Å being a shortest one, Table 1. The same tendency is observed and for other compounds.…”

Section: Description Of the Crystal Structures 1-3mentioning

confidence: 87%

“…Previously, we have obtained the monoradical, [LnRad(NO3)3] (Ln 3+ = Gd, Tb, Dy, Tm [10], and biradical [Ln(Rad)2(OTf)3] (Ln 3+ = Eu and Dy) [11] complexes, where Rad is a tripodal nitroxyl radical (Scheme 1(a)), 4,4-dimethyl-2,2-bis(pyridin-2-yl)-1,3-oxazolidine-3-oxyl. We were somewhat surprised by molar magnetic susceptibility values of 1.78 and 0.348 emuK/mol at 300 and 2 K respectively for the biradical complex, comparing them with those of [Eu(radical)2(anion)3] compounds [12][13][14][15][16][17][18].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Crystal Structure and Spin-Orbit Coupling Analysis for Mono-Scorpionate Eu(III) Complexes

Vostrikova,

Sukhikh,

Lavrov

2023

Preprint

View full text Add to dashboard Cite

Complexes of triply positive europium ion with organic ligands are popular objects for studying photophysical properties. This is related not only to the bright red emission of this 4f element, but also to some spectroscopic peculiarities of its luminescence: the first excited spin-orbit level (7F1) lies only about 300 cm−1 above the ground state (7F0), so that at room temperature its population is around 25–30%. However, such electronic structure of Eu(III) provides its paramagnetism under ordinary conditions. This fact is often ignored by researchers, which is shortsighted from the materials science point of view. A comprehensive and systematic study of the magnetic behavior for the Eu(III) molecular coordination compounds is a challenging task for the development of new polyfunctional materials. The present work presents synthesis, single crystal XRD analysis results, and a magnetic study for the firstly prepared europium(III) complexes with two neutral scorpionate ligands: trispyrazolylmethane (HCPz3) and its methylated analog, tris(3,5-dimethyl-1-pyrazolyl)methane (HC(PzMe2)3). The values of the spin-orbit coupling parameter obtained for Eu-trication by a theoretical approximation of the experimental magnetic susceptibility data are compared with those known for the scarce amount of the magnetically studied molecular compounds.

show abstract

“…The complexes of the 3d metal ions with the radical tripods 34-36 are most of a sandwich type [25][26][27][28][29][30][31][32]137]), while a number of semi-sandwich Ln-complexes were recently synthesized [138,139] (Figure 7-37). In contrast to the tetradentate tripods of TPA described above, the tripodal oxazolidine radical (Rad) 35 is sterically rigid, forming a pyramid upon coordination with an almost right triangle at the face for both monoradical (37) and biradical complexes (38) (Figure 7) [138,140].…”

Section: Complexes Of the Tripodal Nitroxyl Radicalsmentioning

confidence: 96%

Lanthanide Complexes with Tripodal Ligands

Vostrikova¹

2023

Preprint

View full text Add to dashboard Cite

The main property of tripodal ligands is the predictable type of coordination. Homo- and heteroleptic lanthanide complexes with tripodal ligands are a representative class of compounds. However, despite the fact that many of them are paramagnetic their magnetic behavior is poorly understood. This is because their photophysical and catalytic properties have been more attractive. In the present review, we are trying to summarize the available structural information and extremely few data on magnetic properties in order to draw some conclusions about the prospective of tripods using in the design of quantum molecular magnets based on Ln ions. We would like to draw the reader's attention to the fact that despite the consideration of a large part of the currently known lanthanide compounds with tripodal ligands, this review is not exhaustive. However, our goal was to draw the attention of researchers to the fact that a whole niche of air-stable Ln complexes remained outside the attention of magnetochemists and theoreticians.

show abstract

Tripodal Oxazolidine-N-Oxyl Diradical Complexes of Dy3+ and Eu3+

Cited by 8 publications

References 53 publications

Oxazolidine Nitroxide Transformation in a Coordination Sphere of the Ln3+ Ions

Oxazolidine Nitroxide Transformation in a Coordination Sphere of the Ln3+ Ions

Synthesis, Crystal Structure and Spin-Orbit Coupling Analysis for Mono-Scorpionate Eu(III) Complexes

Lanthanide Complexes with Tripodal Ligands

Contact Info

Product

Resources

About