This title appears in the Scientific Report :
2013
Please use the identifier:
http://dx.doi.org/10.1021/ic302309z in citations.
A New Family of Lanthanide Borate Halides with Unusual Coordination and a New Neodymium-Containing Cationic Framework
A New Family of Lanthanide Borate Halides with Unusual Coordination and a New Neodymium-Containing Cationic Framework
The reactions of Ln2O3/CeO2/Pr6O11 (Ln = La–Nd, Sm), molten boric acid, and concentrated HBr or HI result in the formation of La[B7O10(OH)3(H2O)Br], Ln[B6O9(OH)2(H2O)2Br]·0.5H2O (Ln = Ce, Pr), Nd2[B12O17.5(OH)5(H2O)4Br1.5]Br0.5·H2O (NdBOBr), Sm4[B18O25(OH)13Br3], and Ln[B7O11(OH)(H2O)3I] (Ln = La–Nd...
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Personal Name(s): | Polinski, Matthew J. (Corresponding author) |
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Alekseev, Evgeny / Darling, Victoria R. / Cross, Justin N. / Depmeier, Wulf / Albrecht-Schmitt, Thomas E. | |
Contributing Institute: |
Nukleare Entsorgung; IEK-6 |
Published in: | Inorganic chemistry, 52 (2013) 4, S. 1965 - 1975 |
Imprint: |
Washington, DC
American Chemical Society
2013
|
PubMed ID: |
23360290 |
DOI: |
10.1021/ic302309z |
Document Type: |
Journal Article |
Research Program: |
Helmholtz Young Investigators Group: Energy Safety Research for Nuclear Waste Disposal |
Publikationsportal JuSER |
The reactions of Ln2O3/CeO2/Pr6O11 (Ln = La–Nd, Sm), molten boric acid, and concentrated HBr or HI result in the formation of La[B7O10(OH)3(H2O)Br], Ln[B6O9(OH)2(H2O)2Br]·0.5H2O (Ln = Ce, Pr), Nd2[B12O17.5(OH)5(H2O)4Br1.5]Br0.5·H2O (NdBOBr), Sm4[B18O25(OH)13Br3], and Ln[B7O11(OH)(H2O)3I] (Ln = La–Nd, Sm). The lanthanide(III) centers in these compounds are found with 9-coordinate hula hoop or 10-coordinate capped triangular cupola geometries, where there are six approximately coplanar oxygen donors provided by the polyborate sheet. The sheets are formed into three-dimensional frameworks via BO3 triangles that are roughly perpendicular to the layers. Additionally, a new cationic framework, NdBOBr, has been isolated. NdBOBr is unusual in that not only is it a cationic framework, but it is also the first trivalent f-element borate to have terminal halides bound exclusively to the base site of the hula hoop. The Ln[B7O11(OH)(H2O)3I] (Ln = La–Nd, Sm) structures require two corner-shared BO3 units in order to tether the layers together because of the large size of the capping iodine atom. |