Tertiary phosphine oxide complexes of lanthanide diiodides and dibromides

Bannister, Robert D.; Levason, William; Light, Mark E.; Reid, Gillian

doi:10.1016/j.poly.2018.07.057

Cited by 16 publications

(10 citation statements)

References 20 publications

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“…There is no observed 31 P NMR signal for this complex, likely arising from the high magnetic moment from the Eu 2+ center or fluxionality of the ligands around the Eu center. 50 Analysis using 1 H NMR spectroscopy revealed only broad, featureless resonances, attributed to the isopropyl groups, but no other resonances were observed. A high magnetic moment of 9.06 μ B was observed for Eu( tripp BAP) 2 (dme) 2 via the Evans method NMR at room temperature, which is larger than the theoretical value for an Eu 2+ complex, 47,48,51−55 though larger magnetic moments for Eu 2+ have been previously described.…”

Section: ■ Results and Discussionmentioning

confidence: 95%

Magnetism Studies of Bis(acyl)phosphide-Supported Eu³⁺and Eu²⁺Complexes

et al. 2022

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A series of bis(acyl)phosphide-supported Eu complexes were synthesized (bis(acyl)phosphide = BAP). In this study, BAP ligands proved to be excellent ligands for the synthesis of both Eu3+ and Eu2+ molecular complexes. Sodium bis(mesitoyl)phosphide (Na( mes BAP)) and sodium bis(2,4,6-triisopropylbenzoyl)phosphide (Na( tripp BAP)) were employed as ligand precursors for the synthesis of the Eu3+ complexes Eu(bis(mesitoyl)phosphide)3(thf)2 (Eu( mes BAP) 3 (thf) 2 ) and Eu(bis(2,4,6-triisopropylbenzoyl)phosphide)3 (Eu( tripp BAP) 3 ), as well as the Eu2+ complex, Eu(bis(2,4,6-triisopropylbenzoyl)phosphide)2(dme)2 (Eu( tripp BAP) 2 (dme) 2 ) (thf = tetrahydrofuran, dme = 1,2-dimethoxyethane). All complexes were characterized using a combination of UV–vis–NIR–IR and NMR spectroscopies, and single-crystal X-ray diffraction (SC-XRD). The magnetic properties of these three monomeric Eu complexes were investigated by variable-temperature magnetic susceptibility. The magnetic data are typical for these ions, with Eu( tripp BAP) 2 (dme) 2 displaying Curie-type behavior. Both Eu( tripp BAP) 3 and Eu( mes BAP) 3 (thf) 2 possess similar 7F0-7F1 spin–orbit energy gaps and a similar zero-field splitting of the 7F1 state.

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Section: ■ Results and Discussionmentioning

confidence: 95%

Magnetism Studies of Bis(acyl)phosphide-Supported Eu³⁺and Eu²⁺Complexes

et al. 2022

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“…In this regard, several classes of ligands such as cryptands, β-diketones, and carboxylic acids have been applied. Correspondingly, special attention has been paid to phosphoryl-containing ligands, i.e., phosphine oxides and phosphates, because of their established high potential interaction with lanthanide ions. Additionally, the lower vibrational frequencies of the PO bonds rather than CO ones leads to a lesser probability to nonradiative quenching of the lanthanide ions’ excited state .…”

Section: Introductionmentioning

confidence: 99%

Relations between Structural and Luminescence Properties of Novel Lanthanide Nitrate Complexes with Bis-phosphoramidate Ligands

et al. 2019

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Five new bisphosphoramide-based LnIII nitrate complexes [La2(NO3)6L3 I] n (1), [Ce2(NO3)6L3 I] n (2), [Sm2(NO3)6L3 II] n (3), Sm2(NO3)6L3 III (4), and Er(NO3)3L2 III (5) [L I = piperazine-1,4-diylbis(diphenyl phosphine oxide), L II = N,N′-(ethane-1,2-diyl)bis(N-methyl-P,P-diphenylphosphinic amide, and L III = N,N′-(ethane-1,2-diyl)bis(P,P-diphenylphosphinic amide)] have been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), and single crystal X-ray and powder diffractions. The results of the X-ray diffraction analysis revealed the new polymorph of L III , and the structural diversity of the synthesized complexes in the solid state. Complexes 1–3 display two-dimensional coordination polymers (2D-CP), containing layers with honeycomb (6, 3) topology. In these 2D-CPs, each Ln center (La, Ce, and Sm in 1, 2, and 3, respectively) could be considered as a triconnected node, linked by three bridging bisphosphoramide ligands as two-connecting linkers. In contrast, 4 is a discrete binuclear complex, in which bidentate L III ligand has two entirely different conformations: the syn chelating and the anti bridging. Cationic complex 5 shows the monomeric structure, where bidentate L III adopts the syn-chelating conformation. A comprehensive luminescence investigation has been performed on free ligands and their corresponding complexes as well. The synthesized compounds display a variety of luminescence behavior, including the ligand-centered fluorescence in 1, 2, and 5, two distinct emission peaks in 1 and 2, characteristic Sm-centered f–f emission in 3 and 4, and excitation-dependent emission in L III , 1, and 2. Furthermore, the time-dependent density functional theory (TD-DFT) study was carried out on the reported compounds to understand the nature of the emission peaks and the observed luminescence properties. The solid-state emission quantum yields of lanthanide complexes were also determined at different excitation wavelengths.

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“…Introducing tantalum in place of niobium has the obvious consequence of increasing the molecular weight of the corresponding complex by 88 a.m.u.. However, this is unlikely to be the major cause of the failure of the Ta(V) complexes to function as CVD reagents for TaS2, since, based upon the coordination chemistry, the TaOCl3 and TaSCl3 complexes generally appear to be significantly less stable than the niobium analogues, reflecting the harder Lewis acidity of Ta(V) [4,6,7,8,10].…”

Section: Discussionmentioning

confidence: 99%

Chalcogenoether complexes of tantalum(V) sulfide trichloride – Synthesis, properties and structures

et al. 2019

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BuSCH2CH2CH2S n Bu, MeSCH2CH2CH2SMe, MeSeCH2CH2SeMe n BuSeCH2CH2CH2Se n Bu) have been synthesised and isolated in good yield as powdered solids by the reaction of TaCl5 with the appropriate chalcogenoether in a 1:1 molar ratio in anhydrous CH2Cl2 solution at room temperature, followed by the addition of a CH2Cl2 solution containing one mol. equiv. of S(SiMe3)2. The isolated complexes were characterised by IR, 1 H and 77 Se{ 1 H} NMR spectroscopy, as appropriate, and elemental analysis. Single crystal X-ray structure analyses for [TaSCl3(MeSCH2CH2SMe)], [TaSCl3(MeSeCH2CH2SeMe)], [TaSCl3(i PrSCH2CH2S i Pr)] and [TaSCl3(n BuSCH2CH2CH2S n Bu)] have been obtained. The data are compared with the previously described Nb(V) analogues. In contrast to the corresponding [NbSCl3(E n Bu2)] (E = S, Se), attempts to isolate [TaSCl3(E n Bu2)] were unsuccessful. Low pressure chemical vapour deposition (LPCVD) experiments using [TaSCl3(n BuSCH2CH2CH2S n Bu)] did not lead to any deposition, whilst similar experiments using [TaSCl3(n BuSeCH2CH2CH2Se n Bu)] produced only elemental Se films, with no evidence for any deposition of tantalum sulfide or selenide films.

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Tertiary phosphine oxide complexes of lanthanide diiodides and dibromides

Cited by 16 publications

References 20 publications

Magnetism Studies of Bis(acyl)phosphide-Supported Eu³⁺and Eu²⁺Complexes

Magnetism Studies of Bis(acyl)phosphide-Supported Eu³⁺and Eu²⁺Complexes

Relations between Structural and Luminescence Properties of Novel Lanthanide Nitrate Complexes with Bis-phosphoramidate Ligands

Chalcogenoether complexes of tantalum(V) sulfide trichloride – Synthesis, properties and structures

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Tertiary phosphine oxide complexes of lanthanide diiodides and dibromides

Cited by 16 publications

References 20 publications

Magnetism Studies of Bis(acyl)phosphide-Supported Eu3+and Eu2+Complexes

Magnetism Studies of Bis(acyl)phosphide-Supported Eu3+and Eu2+Complexes

Relations between Structural and Luminescence Properties of Novel Lanthanide Nitrate Complexes with Bis-phosphoramidate Ligands

Chalcogenoether complexes of tantalum(V) sulfide trichloride – Synthesis, properties and structures

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Magnetism Studies of Bis(acyl)phosphide-Supported Eu³⁺and Eu²⁺Complexes

Magnetism Studies of Bis(acyl)phosphide-Supported Eu³⁺and Eu²⁺Complexes