Synthesis and Characterization of Solvated Lanthanide Tris(trimethylsilyl)siloxides

Boyle, Timothy J.; Guerrero, Fernando; Cramer, Roger E.; Reuel, Paris C.; Boye, D.M.; Brooks, Henry L.

doi:10.1021/acs.inorgchem.1c03997

Cited by 4 publications

(13 citation statements)

References 71 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Other ligands, such as bridging and terminal alkoxides (entries 7–9), a bidentate nitrate (entry 13), a SiMe 3 -substituted cyclopentadienyl (entry 8), a substituted urea (entry 10), and DMSO (entry 11) all fall within the “nominal Ln-contraction” range. For the 901 structures noted for La, an average La–THF distance of 2.59 Å was observed, while the 418 Lu structures had an average Lu–THF distance of 2.33 Å leading to an average Δ exp = 0.26 Å. Interestingly, this is consistent with the values mentioned above for the [Ln(SST) 3 (THF) 2 ] series (Table , entry 21) . Therefore, the THF coordination to Ln cations exhibits a Ln-contraction 0.08 Å larger than other commonly reported ligands, which display a contraction of 0.18 Å.…”

Section: Resultssupporting

confidence: 84%

“…Exploring additional solvates led us to investigate this trend for the [Ln(SST) 3 (py) 2 ] (Ln = Ce, Eu, and Tm; py = pyridine) structures, which adopted the same TBP geometry and P6 3 space group . For the Ln-ions whose structures are available, Ce and Tm, the decrease in the Ln–O(SST) distance is 2.208–2.088 Å (Δ exp = 0.12 Å), whereas the Ln–N(py) distance ranges from 2.644 to 2.454 (Δ exp = 0.19 Å).…”

Section: Resultsmentioning

confidence: 99%

“…The Lanthanide (Ln) contraction , is a fundamental aspect of the periodic table of elements that is quoted in nearly every textbook covering Ln-based chemistry. − The magnitude of the Ln-contraction is typically reported to range from 0.16 to 0.20 Å, depending on the coordination number of the metal, wherein for a greater coordination number a greater contraction may be observed. , Recently, we reported the structures of the entire Ln-series (minus Pm) for the tetrahydrofuran (THF)-solvated, siloxide derivatives [Ln(SST) 3 (THF) 2 ] [where SST = tris(trimethylsilyl)siloxide (OSi(SiMe 3 ) 3 )], which are potential precursors to LnSiO x materials . The structure of a representative member, [La(SST) 3 (THF) 2 ], is shown in Figure , and select metrical data for these compounds are tabulated in Table .…”

Section: Introductionmentioning

confidence: 99%

“…However, it was not clear if this observation occurred due to differences in chemical bonding between the SST and THF or from some overlooked complication during the crystallographic characterization of these compounds. A potentially confounding factor is that the [Ln(SST) 3 (THF) 2 ] structure is pseudo-centrosymmetric and the THF ligands are disordered over two or three positions, which can complicate analysis . Therefore, in order to further explore this phenomenon, examples of the extreme cations of the Ln-series (La vs Lu) were collected, evaluated, and are compiled in Table , using the Cambridge Crystallographic Data Center’s Cambridge Structural Database (CSD) .…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, in order to further explore this phenomenon, examples of the extreme cations of the Ln-series (La vs Lu) were collected, evaluated, and are compiled in Table , using the Cambridge Crystallographic Data Center’s Cambridge Structural Database (CSD) . This table lists complexes, which are available for identically coordinated and ligated La- and Lu-based molecules. − ,− Note: there was no acceptable matching La and Lu–F structure, so, a matching central core with different pendant ligands was used for entry 5 in Table . The results of this investigation and computation model verification (see Table ) are discussed along with the impact on the Ln-contraction.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

The Lanthanide Contraction Is a Variable

2022

Self Cite

View full text Add to dashboard Cite

Upon examination of the bond distances of the recently reported series of [Ln(SST) 3 (THF) 2 ] [Ln = lanthanides, SST = tris(trimethylsilyl)siloxide (OSi(SiMe 3 ) 3 ), and THF = tetrahydrofuran] compounds, it was found that over the Ln-series (La through Lu), the Ln−O(THF) bond changed by 0.257 Å, whereas the Ln−O(SST) bond varied by 0.164 Å. Examination of all similarly ligated Ln−O(THF) (Ln = La vs Lu) structures available in the Cambridge Structural Database (CSD) revealed that this previously unreported, increased Ln-contraction is pervasive. Further evaluations showed that this enhanced Lncontraction also occurs for pyridine (py) in the [Ln(SST) 3 (py) 2 ] family as well as the average Ln−N(py) (La vs Lu) structure distances recovered from the CSD. Additional ligands, such as halides (Cl and I) were found to display this enhanced Lncontraction, while other species (i.e., cyclopentadienide, alkoxide, SST, and dimethyl sulfoxide) yielded a "normal" Ln-contraction (La−L vs Lu−L). Gas-phase electronic structure density functional theory calculations were carried out to evaluate the molecular orbital influence on the Ln-contraction between Ln−O(SST) and Ln−O(THF). The calculated [Ln(SST) 3 (THF) 2 ] structures were found to demonstrate the same capricious Ln-contraction. Based on these studies, one can say that the variability of the Lncontraction noted in the [Ln(SST) 3 (THF) 2 ] experimental data is due to the different bonding types, ion−ion for the Ln−SST bond versus ion−dipole for the Ln−THF bond.

show abstract

Section: Resultssupporting

confidence: 84%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

The Lanthanide Contraction Is a Variable

2022

Self Cite

View full text Add to dashboard Cite

show abstract

Luminescence and Single‐Molecule Magnet Properties in Ideal Symmetry Compounds: Example of a Near‐Planar Tricoordinate Ytterbium(III) Amide

Jain,

Houard,

Marchal

et al. 2024

ChemistryEurope

View full text Add to dashboard Cite

We are reporting on the use of a low‐coordinate YbIII amide with near‐ideal planar trigonal [Yb{N(SiMe3)2}3] (1) and on a bipyramidal trigonal derivative [Yb{N(SiMe2H)2}3 ⋅ (thf)2] (2) that constitute quintessential cases to investigate luminescent and magnetic properties otherwise usually blurred on less symmetrical compounds. These compounds represent the first experimental objects that allow for the confirmation of the recent conjecture about best‐performing SMM built on the archetypal prolate lanthanide ion. We have performed a combined theoretical, luminescent, and magnetic study on these molecules. For 1, a spectacular split of the 2F7/2 ground state of 1312 cm−1 is measured by low‐temperature near‐infra‐red luminescence as well as the calculated pure wavefunction composition of the low‐lying Kramers doublets, making this complex a textbook example of a prolate SMM. These results are corroborated by comparison with 2, that exhibits as expected a 50 % decrease of the ground state splitting compared to 1. Yet, we show that these remarkable features are insufficient to promote SMM behavior, and Orbach relaxation is unlikely to occur even on such an ideal low‐coordinate SMM without control of spin‐phonon coupling.

show abstract