Anion dependent ion pairing in concentrated ytterbium halide solutions

Klinkhammer, Christina; Böhm, Fabian; Sharma, Vinay; Schwaab, Gerhard; Seitz, Michael; Havenith, Martina

doi:10.1063/1.5016549

Cited by 10 publications

(9 citation statements)

References 60 publications

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“…However, the fraction of the chloro-complex diminishes rapidly upon dilution and at a concentration < 0.4 mol·L −1 , the chloro-complex species vanished. Our Raman spectroscopic findings were substantiated by recently published EXAFS and terahertz FT-IR and results [34,35].…”

Section: Discussionsupporting

confidence: 86%

“…In solutions with an excess of LiCl, it was demonstrated that inner sphere chloro-complexation takes place together with a loss of water [34]. Furthermore, a current study in the terahertz frequency range of YbCl 3 solutions using FT-IR spectroscopy [35] confirmed weak contact ion pairs as do our recent Raman results on LuCl 3 (aq) [17]. Choppin and Unrein [36] claimed that only outer-sphere ions pairs exist in lanthanide chloride solutions, but such a view has been questioned [17,29,30,31,32].…”

Section: Resultsmentioning

confidence: 99%

“…In dilute solutions (C T < 0.4 mol·L −1 ) the chloro-complex species disappeared upon dilution and [Yb(OH 2 ) 8 ] 3+ and Cl − (aq) formed. The chloro-complex formation may be one reason for the data scatter of the recently published Yb–O bond distances and coordination numbers presented for Yb 3+ (aq) and other rare earth chloride systems [35,36]. In recent experimental structural studies, it was observed that inner-sphere chloro-complex species are formed in aqueous LnCl 3 solution (Ln = Lu and Yb) with high chloride concentrations while in dilute solutions, fully hydrated ions exist [17,34,35].…”

Section: Resultsmentioning

confidence: 99%

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On the Hydration of Heavy Rare Earth Ions: Ho3+, Er3+, Tm3+, Yb3+ and Lu3+—A Raman Study

Rudolph

Irmer

2019

Molecules

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Raman spectra of aqueous Ho3+, Er3+, Tm3+, Yb3+, and Lu3+-perchlorate solutions were measured over a large wavenumber range from 50–4180 cm−1. In the low wavenumber range (terahertz region), strongly polarized Raman bands were detected at 387 cm−1, 389 cm−1, 391 cm−1, 394 cm−1, and 396 cm−1, respectively, which are fairly broad (full widths at half height at ~52 cm−1). These isotropic Raman bands were assigned to the breathing modes, ν1 Ln–O of the heavy rare earth (HRE) octaaqua ions, [Ln(H2O)8]3+. The strong polarization of these bands (depolarization degree ~0) reveals their totally symmetric character. The vibrational isotope effect was measured in Yb(ClO4)3 solutions in H2O and D2O and the shift of the ν1 mode in changing from H2O to D2O further supports the character of the band. The Ln–O bond distances of these HRE ions (Ho3+, Er3+, Tm3+, Yb3+, and Lu3+) follow the order of Ho–O > Er–O > Tm–O > Yb–O > Lu–O which correlates inversely with the band positions of the breathing modes of their corresponding octaaqua ions [Ln(OH2)8]3+. Furthermore, the force constants, kLn–O, were calculated for these symmetric stretching modes. Ytterbium perchlorate solutions were measured over a broad concentration range, from 0.240 mol·L−1 to 2.423 mol·L−1, and it was shown that with increasing solute concentration outer-sphere ion pairs and contact ion pairs were formed. At the dilute solution state (~0.3 mol·L−1), the fully hydrated ions [Yb(H2O)8]3+ exist, while at higher concentrations (CT > 2 mol·L−1), ion pairs are formed. The concentration behavior of Yb(ClO4)3 (aq) shows similar behavior to the one observed for La(ClO4)3(aq), Ce(ClO4)3(aq) and Lu(ClO4)3(aq) solutions. In ytterbium chloride solutions in water and heavy water, representative for the behavior of the other HRE ions, 1:1 chloro-complex formation was detected over the concentration range from 0.422–3.224 mol·L−1. The 1:1 chloro-complex in YbCl3(aq) is very weak, diminishing rapidly with dilution and vanishing at a concentration < 0.4 mol·L−1.

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Section: Discussionsupporting

confidence: 86%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

On the Hydration of Heavy Rare Earth Ions: Ho3+, Er3+, Tm3+, Yb3+ and Lu3+—A Raman Study

Rudolph

Irmer

2019

Molecules

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“…Further experimental support for Lu 3+ - chloride complex formation stems from a recent THz FTIR study on a similar system, YbCl 3 (aq) and YbBr 3 (aq). While in YbCl 3 (aq) chloro-complex species albeit weak are formed no such species exist in the bromide system [66].…”

Section: Resultsmentioning

confidence: 99%

Hydration and Ion Pair Formation in Aqueous Lu3+- Solution

Rudolph

Irmer

2018

Molecules

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Aqueous solutions of Lu3+- perchlorate, triflate and chloride were measured by Raman spectroscopy. A weak, isotropic mode at 396 cm−1 (full width at half height (fwhh) at 50 cm−1) was observed in perchlorate and triflate solutions. This mode was assigned to the totally symmetric stretching mode of [Lu(OH2)8]3+, ν1LuO8. In Lu(ClO4)3 solutions in heavy water, the ν1LuO8 symmetric stretch of [Lu(OD2)8]3+ appears at 376.5 cm−1. The shift confirms the theoretical isotopic effect of this mode. In the anisotropic scattering of aqueous Lu(ClO4)3, five bands of very low intensity were observed at 113 cm−1, 161.6 cm−1, 231 cm−1, 261.3 cm−1 and 344 cm−1. In LuCl3 (aq) solutions measured over a concentration range from 0.105–3.199 mol·L−1 a 1:1 chloro-complex was detected. Its equilibrium concentration, however, disappeared rapidly with dilution and vanished at a concentration < 0.5 mol·L−1. Quantitative Raman spectroscopy allowed the detection of the fractions of [Lu(OH2)8]3+, the fully hydrated species and the mono-chloro complex, [Lu(OH2)7Cl]2+. In a ternary LuCl3/HCl solution, a mixtrure of chloro-complex species of the type [Lu(OH2)8−nCln]+3−n (n = 1 and 2) were detected. DFT geometry optimization and frequency calculations are reported for Lu3+- water cluster in vacuo and with a polarizable dielectric continuum (PC) model including the bulk solvent implicitly. The bond distance and angle for [Lu(OH2)8]3+ within the PC are in good agreement with data from structural experiments. The DFT frequencies for the Lu-O modes of [Lu(OH2)8]3+ and its deuterated analog [Lu(OD2)8]3+ in a PC are in fair agreement with the experimental ones. The calculated hydration enthalpy of Lu3+ (aq) is slightly lower than the experimental value.

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“…Alternatively, a novel ratiometric detection strategy can in some cases be used to obtain hydration-shell spectra that are essentially identical to the SC spectra obtained using SMCR . Moreover, vibrational terahertz (THz) difference spectroscopy has been extensively used by the Havenith group − and others , to resolve low-frequency IR hydration-shell spectra. Some of the results obtained using the above methods are further described in the following subsections (as well as in the papers cited above, and references therein).…”

Section: Discussionmentioning

confidence: 99%

Hydration-Shell Vibrational Spectroscopy

Ben‐Amotz

2019

J. Am. Chem. Soc.

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Hydration-shell vibrational spectroscopy provides an experimental window into solute-induced water structure changes that mediate aqueous folding, binding, and self-assembly. Decomposition of measured Raman and infrared (IR) spectra of aqueous solutions using multivariate curve resolution (MCR) and related methods may be used to obtain solute-correlated spectra revealing solute-induced perturbations of water structure, such as changes in water hydrogen-bond strength, tetrahedral order, and the presence of dangling (non-hydrogen-bonded) OH groups. More generally, vibrational-MCR may be applied to both aqueous and nonaqueous solutions, including multicomponent mixtures, to quantify solvent-mediated interactions between oily, polar, and ionic solutes, in both dilute and crowded fluids. Combining vibrational-MCR with emerging theoretical modeling strategies promises synergetic advances in the predictive understanding of multiscale self-assembly processes of both biological and technological interest.

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Anion dependent ion pairing in concentrated ytterbium halide solutions

Cited by 10 publications

References 60 publications

On the Hydration of Heavy Rare Earth Ions: Ho3+, Er3+, Tm3+, Yb3+ and Lu3+—A Raman Study

On the Hydration of Heavy Rare Earth Ions: Ho3+, Er3+, Tm3+, Yb3+ and Lu3+—A Raman Study

Hydration and Ion Pair Formation in Aqueous Lu3+- Solution

Hydration-Shell Vibrational Spectroscopy

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