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Molecules 2018, 23(12), 3237; https://doi.org/10.3390/molecules23123237

Hydration and Ion Pair Formation in Aqueous Lu3+- Solution

1
Medizinische Fakultät der TU Dresden, Institut für Virologie im MTZ, Fiedlerstr. 42, 01307 Dresden, Germany
2
Technische Universität Bergakademie Freiberg, Institut für Theoretische Physik, Leipziger Str. 23, 09596 Freiberg, Germany
*
Author to whom correspondence should be addressed.
Received: 19 November 2018 / Revised: 3 December 2018 / Accepted: 3 December 2018 / Published: 7 December 2018
(This article belongs to the Special Issue Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife')
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Abstract

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. View Full-Text
Keywords: Raman spectroscopy; Lu(ClO4)3; Lu(CF3SO3)3 and LuCl3 solutions in H2O and D2O; Lu3+- hydration; Lu-O skeleton modes; monochloro complex of Lu3+; DFT calculations of [Lu(OH2)8]3+; polarizable dielectric continuum model Raman spectroscopy; Lu(ClO4)3; Lu(CF3SO3)3 and LuCl3 solutions in H2O and D2O; Lu3+- hydration; Lu-O skeleton modes; monochloro complex of Lu3+; DFT calculations of [Lu(OH2)8]3+; polarizable dielectric continuum model
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Rudolph, W.; Irmer, G. Hydration and Ion Pair Formation in Aqueous Lu3+- Solution. Molecules 2018, 23, 3237.

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