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Title: Electrostatic Interactions versus Second Order Jahn–Teller Distortion as the Source of Structural Diversity in Li 3 MO 4 Compounds (M = Ru, Nb, Sb and Ta)

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [3];  [3];  [1]
  1. Collège de France, Chaire de Chimie du Solide et de l’Energie, UMR 8260, 11 place Marcelin Berthelot, 75231 CEDEX 05, Paris, France; Sorbonne Universités − UPMC Univ. Paris 06, 4 place Jussieu, F-75005, Paris, France; Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459, 80039, Amiens, France
  2. Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459, 80039, Amiens, France
  3. Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459, 80039, Amiens, France; Institut Charles Gerhardt, CNRS UMR 5253, Université Montpellier, Place E. Bataillon, 34 095, Montpellier, France
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
FOREIGN
OSTI Identifier:
1419871
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chemistry of Materials; Journal Volume: 30; Journal Issue: 2
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Jacquet, Quentin, Rousse, Gwenaëlle, Iadecola, Antonella, Saubanère, Matthieu, Doublet, Marie-Liesse, and Tarascon, Jean-Marie. Electrostatic Interactions versus Second Order Jahn–Teller Distortion as the Source of Structural Diversity in Li 3 MO 4 Compounds (M = Ru, Nb, Sb and Ta). United States: N. p., 2018. Web. doi:10.1021/acs.chemmater.7b04117.
Jacquet, Quentin, Rousse, Gwenaëlle, Iadecola, Antonella, Saubanère, Matthieu, Doublet, Marie-Liesse, & Tarascon, Jean-Marie. Electrostatic Interactions versus Second Order Jahn–Teller Distortion as the Source of Structural Diversity in Li 3 MO 4 Compounds (M = Ru, Nb, Sb and Ta). United States. doi:10.1021/acs.chemmater.7b04117.
Jacquet, Quentin, Rousse, Gwenaëlle, Iadecola, Antonella, Saubanère, Matthieu, Doublet, Marie-Liesse, and Tarascon, Jean-Marie. 2018. "Electrostatic Interactions versus Second Order Jahn–Teller Distortion as the Source of Structural Diversity in Li 3 MO 4 Compounds (M = Ru, Nb, Sb and Ta)". United States. doi:10.1021/acs.chemmater.7b04117.
@article{osti_1419871,
title = {Electrostatic Interactions versus Second Order Jahn–Teller Distortion as the Source of Structural Diversity in Li 3 MO 4 Compounds (M = Ru, Nb, Sb and Ta)},
author = {Jacquet, Quentin and Rousse, Gwenaëlle and Iadecola, Antonella and Saubanère, Matthieu and Doublet, Marie-Liesse and Tarascon, Jean-Marie},
abstractNote = {},
doi = {10.1021/acs.chemmater.7b04117},
journal = {Chemistry of Materials},
number = 2,
volume = 30,
place = {United States},
year = 2018,
month = 1
}
  • We have approached the synthesis of discrete fulleride salts, through the use of strongly reducing organometallic species such as metallocenes, which allow precise control of stoichiometry for the production of C{sub 60}{sup n-} species. Decamethylnickelocene Ni(C{sub 5}Me{sub 5}){sub 2}, is a selective reductant for the production of C{sub 60} monoanion and yields a crystalline 1:1 salt when combined with C{sub 60} in CS{sub 2}. The structure of this salt [Ni(C{sub 5}Me{sub 5}) {sub 2}{sup +}][C{sub 60}{sup -}].CS{sub 2} (1), is highly ordered and is the first example of a non-disordered monoanionic C{sub 60} structure. We report here the synthesis andmore » single-crystal X-ray structure of 1 and structural evidence for the expected Jahn-Teller distortion in the C{sub 60} monoanion. 16 refs., 3 figs.« less
  • X-ray structure determinations are reported for the (tetraphenylporphyrinato)iron(III) complexes of the substituted imidazole ligands cis- and trans-methylurocanate (cMU and tMU, respectively). Both complexes are six-coordinate and low-spin. The cMU ligand has an internal hydrogen bond, while the tMU ligand is hydrogen bonded to a THF solvate molecule. Crystals of the cMU complex contain two crystallographically independent centrosymmetric cations; these species differ in the orientation of the imidazole ligands with respect to the porphyrin. Single-crystal EPR g-tensor determinations for the two forms of the cMU complex reveal the ligand orientation influences both the distribution of spin density in the complex andmore » the energies of the highest occupied molecular orbitals. This influence appears to arise in part from the direct interaction between metal and axial ligand ..pi.. orbitals and in part through pseudo-Jahn-Teller induced distortion of the porphyrin ligand. Crystal data: FeTPP(cMU)/sub 2/SbF/sub 6/ x 1.5toluene, space group P1 vector, Z = 2, a = 10.406 (5) A, b = 11.752 (4) A, c = 28.538 (10 A, ..cap alpha.. = 103.34 (3)/sup 0/, ..beta.. = 108.35 (3)/sup 0/, ..gamma.. = 106.18 (3)/sup 0/ at 115 K; FeTPP(tMU)/sub 2/SbF/sub 6/ x 2THF, space group P1 vector, Z = 1, a = 9.898 (3) A, b = 12.600 (4) A, c = 15.344 (8) A, ..cap alpha.. = 99.99 (3)/sup 0/,..beta.. = 112.82 (3)/sup 0/, ..gamma.. = 114.58 (2) at 115 K.« less
  • The variation of the EPR spectra with degree of deuteration of the partially deuterated Tutton salt ammonium hexaaquacopper(II) sulfate, (NH{sub 4}){sub 2}[Cu(H{sub 2}O){sub 6}](SO{sub 4}){sub 2}, has been measured at 293 K. The measurements indicate that the structure changes quite abruptly from that of the pure hydrogenous salt to that of the fully deuterated salt at {approximately}50% deuteration. The structure of a crystal in which {approximately}42% of the hydrogen atoms were replaced by deuterium was elucidated at 15 K by single-crystal time-of-flight neutron diffraction. The hexaaquacopper(II) complex exhibits an orthorhombically distorted, tetragonally elongated octahedral coordination geometry (Cu-O bond distances ofmore » 2.281(1), 2.007(1), and 1.975(1){angstrom}). The structure is very similar to that reported for the undeuterated salt at 9.6 K, and markedly different from that of the fully deuterated compound at 15 K, which has similar Cu-O bond lengths but with the directions of the long and intermediate bonds interchanged. There is no evidence for disorder or partial switching of the Cu-O bond directions. This is consistent with the temperature dependence of the EPR spectrum of the {approximately}42% deuterated compound, which indicates a thermal equilibrium between the two structural forms close to room temperature similar to that reported for the undeuterated compound, but complete reversion to the low-temperature phase on cooling to 5 K. The possible influence of deuteration upon the hydrogen-bonding distances and the bearing of this upon the structural modifications of the compound are discussed.« less