Electronic structures of bent lanthanide(III) complexes with two N-donor ligands

Nicholas, Hannah M.; Vonci, Michele; Goodwin, Conrad A. P.; Loo, Song Wei; Murphy, S C; Cassim, Daniel; Winpenny, Richard E. P.; McInnes, Eric J. L.; Chilton, Nicholas F.; Mills, David P.

doi:10.1039/c9sc03431e

Cited by 29 publications

(34 citation statements)

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“…Thereby, the Ce–P distances are slightly longer than in previously reported Ce(III) phosphine complexes, , but are in the same range as the recently reported complexes by Schelter et al A similar elongation is also observed for the Ln1–N1 bonds from 2.373(3) Å in 1-La to 2.436(3) Å in 8-La and from 2.333(3) Å in 1-Ce to 2.408(4) Å in 8-Ce . The distances of the lanthanide atom to the silylamide nitrogen atoms in 8-La and 8-Ce are in the range of previously reported Ln(HMDS) x complexes. ,− For further crystallographic information see the Supporting Information, Tables S1–S5.…”

Section: Resultsmentioning

confidence: 66%

Monoanionic Anilidophosphine Ligand in Lanthanide Chemistry: Scope, Reactivity, and Electrochemistry

et al. 2020

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We present the synthesis of a series of new lanthanide(III) complexes supported by a monoanionic bidentate anilidophosphine ligand (N-(2-(diisopropylphosphanyl)-4-methylphenyl)-2,4,6-trimethylanilide, short PN − ). The work comprises the characterization of a variety of heteroleptic complexes containing either one or two PN ligands as well as a study on further functionalization possibilities. The new heteroleptic complexes cover selected examples over the whole lanthanide(III) series including lanthanum, cerium, neodymium, gadolinium, terbium, dysprosium, and lutetium. In case of the two diamagnetic metal cations lanthanum(III) and lutetium(III), we have furthermore studied the influence of the lanthanide ion (early vs. late) on the reactivity of these complexes. Thereby we found that the radius of the lanthanide ion has a major influence on the reactivity. Using sterically demanding, multidentate ligand systems, e.g., cyclopentadienide (Cp − ), we found that the lanthanum complex La(PN) 2 Cl (1-La) reacts well to the corresponding cyclopentadienide complex, while for Lu(PN) 2 Cl (1-Lu) no reaction was observed under any conditions tested. On the contrary, employing monodentate ligands such as mesitolate, thiomesitolate, 2,4,6-trimethylanilide or 2,4,6-trimethylphenylphosphide, results in the clean formation of the desired complexes for both lanthanum and lutetium. All complexes have been studied by various techniques, including multi nuclear NMR spectroscopy and X-ray crystallography. 31 P NMR spectroscopy was furthermore used to evaluate the presence of open coordination sites on the complexes using coordinating and noncoordinating solvents, and as a probe for estimating the Ce−P distance in the corresponding complexes. Additionally, we present cyclic voltammetry (CV) data for Ce(PN) 2 Cl (1-Ce), La(PN) 2 Cl (1-La), Ce(PN)(HMDS) 2 (8-Ce) and La(PN)(HMDS) 2 (8-La) (with HMDS = hexamethyldisilazide, (Me 3 Si) 2 N − ) exploring the potential of the anilidophosphane ligand framework to stabilize a potential Ce(IV) ion.

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Section: Resultsmentioning

confidence: 66%

Monoanionic Anilidophosphine Ligand in Lanthanide Chemistry: Scope, Reactivity, and Electrochemistry

et al. 2020

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“…In recent years, lanthanide ion (Ln 3+ )-based PBAs have attracted a great deal of attention due to their unique properties, allowing them to generate new physicochemical effects that are not available for d-block paramagnetic metal complexes. The presence of shielded f-electron ions enables them to acquire properties such as luminescence and high magnetic anisotropy associated with slow magnetic relaxation processes. − Therefore, these assemblies are predisposed to demonstrate strong optical emission and single-molecule magnet (SMM) behaviors. − …”

Section: Introductionmentioning

confidence: 99%

Magnetic Properties and Second Harmonic Generation of Noncentrosymmetric Cyanido-Bridged Ln(III)–W(V) Assemblies

et al. 2021

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One-dimensional zigzag cyanido-bridged coordination polymers have been prepared as a result of self-assembly of lanthanide(III) ions with octacyanidotungstate(V) anions in the presence of N,N-dimethylacetamide (dma). All compounds crystallized in noncentrosymmetric space group P21 with a molecular formula of [LnIII(dma)5][WV(CN)8] [Ln = Gd (1), Tb (2), Dy (3), Ho (4), Er (5), Tm (6), Yb (7), Lu (8), or Y (9)]. Magnetic studies revealed weak antiferromagnetic interactions through LnIII–NC–WV bridges and the formation of ferrimagnetically coupled chains at very low temperatures. Moreover, temperature dependencies of magnetic susceptibilities were fitted using the crystal field parameters for Ln(III) ions, determined by the ab initio calculations, yielding magnetic coupling constants in the range of −1 to −5 cm–1. The wide optical transparency of 1–9 has been determined using solid state absorption spectroscopy. Samples exhibited second harmonic (SH) generation properties with SH susceptibilities ranging from 4.7 × 10–12 to 9.4 × 10–11 esu due to the presence of nonlinear optical susceptibility tensor elements (χ ijk ) χ zxx , χ zyy , χ zzz , χ zxy , χ yyz , χ yzx , χ xyz , and χ xzx , corresponding to space group P21. The determined values were also compared with the results of theoretical calculations and previous reports, indicating a potential relationship between the type of lanthanide ion and the SH intensity.

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“…Room temperature solution phase magnetic moments determined for 1-E and 2-E 2 using the Evans method are consistent with other Sm(III)-N †† species (Table ). − , The solution moments for 1-E are higher than the room temperature χ M T products that range 0.14–0.19 cm 3 K mol –1 from magnetometric measurements on powder samples, though both are noticeably larger than the free-ion value for a 6 H 5/2 multiplet at 0.09 cm 3 K mol –1 . This is characteristic of Sm(III), where the observed moment is dominated by temperature independent paramagnetism from second-order mixing with low-lying excited states. , On cooling, χ M T steadily decreases to 0.03 cm 3 K mol –1 at 2 K (Figures S45, S47, and S49).…”

Section: Resultsmentioning

confidence: 90%

“…There are numerous examples of analogous reactions across the f block, ,,, and these polar M–ER groups (M = Ln or An) are amenable to further derivatization . We have previously shown that although the ligand framework in [Sm(N †† ) 2 ] is sterically demanding, the two bis(triisopropylsilyl)amide ligands are flexible enough to bend toward each other to accommodate further moieties at the Sm center, thus we envisaged that this redox strategy would afford a series of structurally similar complexes. ,, Gratifyingly, the separate reactions of [Sm(N †† ) 2 ] with half an equivalent of E 2 Ph 2 in toluene gave the heteroleptic Sm(III) complexes [Sm(N †† ) 2 (EPh)] (E = S, 1-S ; Se, 1-Se ; Te, 1-Te ; Scheme ) in moderate to excellent yields (52–93%). Previously, Ln–EPh moieties have been investigated toward reductive elimination of E 2 Ph 2 in order to access Ln redox chemistry while avoiding the challenging synthesis of divalent precursors …”

Section: Resultsmentioning

confidence: 99%

Heteroleptic Samarium(III) Chalcogenide Complexes: Opportunities for Giant Exchange Coupling in Bridging σ- and π-Radical Lanthanide Dichalcogenides

et al. 2020

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The introduction of (N2)3–• radicals into multinuclear lanthanide molecular magnets raised hysteresis temperatures by stimulating strong exchange coupling between spin centers. Radical ligands with larger donor atoms could promote more efficient magnetic coupling between lanthanides to provide superior magnetic properties. Here, we show that heavy chalcogens (S, Se, Te) are primed to fulfill these criteria. The moderately reducing Sm(II) complex, [Sm(N††)2], where N†† is the bulky bis(triisopropylsilyl)amide ligand, can be oxidized (i) by diphenyldichalcogenides E2Ph2 (E = S, Se, Te) to form the mononuclear series [Sm(N††)2(EPh)] (E = S, 1-S; Se, 1-Se, Te, 1-Te); (ii) S8 or Se8 to give dinuclear [{Sm(N††)2}2(μ-η2:η2-E2)] (E = S, 2-S2 ; Se, 2-Se2 ); or (iii) with TePEt3 to yield [{Sm(N††)2}(μ-Te)] (3). These complexes have been characterized by single crystal X-ray diffraction, multinuclear NMR, FTIR, and electronic spectroscopy; the steric bulk of N†† dictates the formation of mononuclear complexes with chalcogenate ligands and dinuclear species with the chalcogenides. The Lα1 fluorescence-detected X-ray absorption spectra at the Sm L3-edge yielded resolved pre-edge and white-line peaks for 1-S and 2-E 2 , which served to calibrate our computational protocol in the successful reproduction of the spectral features. This method was employed to elucidate the ground state electronic structures for proposed oxidized and reduced variants of 2-E 2 . Reactivity is ligand-based, forming species with bridging superchalcogenide (E2)−• and subchalcogenide (E2)3–• radical ligands. The extraordinarily large exchange couplings provided by these dichalcogenide radicals reveal their suitability as potential successors to the benchmark (N2)3–• complexes in molecular magnets.

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Electronic structures of bent lanthanide(III) complexes with two N-donor ligands

Cited by 29 publications

References 50 publications

Monoanionic Anilidophosphine Ligand in Lanthanide Chemistry: Scope, Reactivity, and Electrochemistry

Monoanionic Anilidophosphine Ligand in Lanthanide Chemistry: Scope, Reactivity, and Electrochemistry

Magnetic Properties and Second Harmonic Generation of Noncentrosymmetric Cyanido-Bridged Ln(III)–W(V) Assemblies

Heteroleptic Samarium(III) Chalcogenide Complexes: Opportunities for Giant Exchange Coupling in Bridging σ- and π-Radical Lanthanide Dichalcogenides

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