%0 Journal Article %1 flosbach_stabilization_2024 %A Flosbach, Niko T. %A Bykov, Maxim %A Bykova, Elena %A Rasche, Bertold %A Mezouar, Mohamed %A Fedotenko, Timofey %A Chariton, Stella %A Prakapenka, Vitali B. %A Wickleder, Mathias S. %D 2024 %J Inorg. Chem. %K imported myown %R 10.1021/acs.inorgchem.3c03948 %T Stabilization of Pr4+ in Silicates─High-Pressure Synthesis of PrSi3O8 and Pr2Si7O18 %U https://doi.org/10.1021/acs.inorgchem.3c03948 %X The reaction between PrO2 and SiO2 was investigated at various pressure points up to 29 GPa in a diamond anvil cell using laser heating and in situ single-crystal structure analysis. The pressure points at 5 and 10 GPa produced Pr2III(Si2O7), whereas Pr4IIISi3O12 and Pr2IV(O2)O3 were obtained at 15 GPa. Pr4IIISi3O12 can be interpreted as a high-pressure modification of the still unknown orthosilicate Pr4III(SiO4)3. PrIVSi3O8 and Pr2IVSi7O18 that contain praseodymium in its rare + IV oxidation state were identified at 29 GPa. After the pressure was released from the reaction chamber, the Pr(IV) silicates could be recovered, indicating that they are metastable at ambient pressure. Density functional theory calculations of the electronic structure corroborate the oxidation state of praseodymium in both PrIVSi3O8 and Pr2IVSi7O18. Both silicates are the first structurally characterized representatives of Pr4+-containing salts with oxoanions. All three silicates contain condensed networks of SiO6 octahedra which is unprecedented in the rich chemistry of lanthanoid silicates.

@article{flosbach_stabilization_2024, abstract = {The reaction between PrO2 and SiO2 was investigated at various pressure points up to 29 GPa in a diamond anvil cell using laser heating and in situ single-crystal structure analysis. The pressure points at 5 and 10 GPa produced Pr2III(Si2O7), whereas Pr4IIISi3O12 and Pr2IV(O2)O3 were obtained at 15 GPa. Pr4IIISi3O12 can be interpreted as a high-pressure modification of the still unknown orthosilicate Pr4III(SiO4)3. PrIVSi3O8 and Pr2IVSi7O18 that contain praseodymium in its rare + IV oxidation state were identified at 29 GPa. After the pressure was released from the reaction chamber, the Pr(IV) silicates could be recovered, indicating that they are metastable at ambient pressure. Density functional theory calculations of the electronic structure corroborate the oxidation state of praseodymium in both PrIVSi3O8 and Pr2IVSi7O18. Both silicates are the first structurally characterized representatives of Pr4+-containing salts with oxoanions. All three silicates contain condensed networks of [SiO6] octahedra which is unprecedented in the rich chemistry of lanthanoid silicates.}, added-at = {2024-03-25T12:35:57.000+0100}, author = {Flosbach, Niko T. and Bykov, Maxim and Bykova, Elena and Rasche, Bertold and Mezouar, Mohamed and Fedotenko, Timofey and Chariton, Stella and Prakapenka, Vitali B. and Wickleder, Mathias S.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/24feff6e2b88fd8d415145c2b4a90948a/brasche}, doi = {10.1021/acs.inorgchem.3c03948}, file = {Flosbach et al_2024_Stabilization of Pr4+ in Silicates─High-Pressure Synthesis of PrSi3O8 and.pdf:files/7124/Flosbach et al_2024_Stabilization of Pr4+ in Silicates─High-Pressure Synthesis of PrSi3O8 and.pdf:application/pdf}, interhash = {f9bba58cf305054f14ad9fe827a01c5c}, intrahash = {4feff6e2b88fd8d415145c2b4a90948a}, issn = {0020-1669}, journal = {Inorg. Chem.}, keywords = {imported myown}, month = feb, note = {Publisher: American Chemical Society}, timestamp = {2024-03-25T12:38:29.000+0100}, title = {Stabilization of {Pr4}+ in {Silicates}─{High}-{Pressure} {Synthesis} of {PrSi3O8} and {Pr2Si7O18}}, url = {https://doi.org/10.1021/acs.inorgchem.3c03948}, urldate = {2024-03-04}, year = 2024 }