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Jepsen LH, Ley MB, Černý R, et al. Trends in Syntheses, Structures, and Properties for Three Series of Ammine Rare-Earth Metal Borohydrides, M(BH4)3·nNH3 (M = Y, Gd, and Dy). Inorg Chem. 2015;54(15):7402-14doi: 10.1021/acs.inorgchem.5b00951.
Jepsen, L. H., Ley, M. B., Černý, R., Lee, Y. S., Cho, Y. W., Ravnsbæk, D., Besenbacher, F., Skibsted, J., & Jensen, T. R. (2015). Trends in Syntheses, Structures, and Properties for Three Series of Ammine Rare-Earth Metal Borohydrides, M(BH4)3·nNH3 (M = Y, Gd, and Dy). Inorganic chemistry, 54(15), 7402-14. https://doi.org/10.1021/acs.inorgchem.5b00951
Jepsen, Lars H, et al. "Trends in Syntheses, Structures, and Properties for Three Series of Ammine Rare-Earth Metal Borohydrides, M(BH4)3·nNH3 (M = Y, Gd, and Dy)." Inorganic chemistry vol. 54,15 (2015): 7402-14. doi: https://doi.org/10.1021/acs.inorgchem.5b00951
Jepsen LH, Ley MB, Černý R, Lee YS, Cho YW, Ravnsbæk D, Besenbacher F, Skibsted J, Jensen TR. Trends in Syntheses, Structures, and Properties for Three Series of Ammine Rare-Earth Metal Borohydrides, M(BH4)3·nNH3 (M = Y, Gd, and Dy). Inorg Chem. 2015 Aug 03;54(15):7402-14. doi: 10.1021/acs.inorgchem.5b00951. Epub 2015 Jul 21. PMID: 26196159.
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Inorg Chem. 2015 Aug 03;54(15):7402-14. doi: 10.1021/acs.inorgchem.5b00951. Epub 2015 Jul 21.

Trends in Syntheses, Structures, and Properties for Three Series of Ammine Rare-Earth Metal Borohydrides, M(BH4)3·nNH3 (M = Y, Gd, and Dy).

Inorganic chemistry

Lars H Jepsen, Morten B Ley, Radovan Černý, Young-Su Lee, Young Whan Cho, Dorthe Ravnsbæk, Flemming Besenbacher, Jørgen Skibsted, Torben R Jensen

Affiliations

  1. †Center for Materials Crystallography, Interdisciplinary Nanoscience Center and Department of Chemistry, Aarhus University, Langelandsgade 140, 8000 Aarhus C, Denmark.
  2. ‡Laboratory of Crystallography, DQMP, University of Geneva, 1211 Geneva, Switzerland.
  3. §High Temperature Energy Materials Research Center, Korea Institute of Science and Technology, Seoul 136-791, Republic of Korea.
  4. ?Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, Odense M 5230, Denmark.
  5. ?Interdisciplinary Nanoscience Center (iNANO) and Department of Physics and Astronomy, Aarhus University, Ny Munkegade 120, Aarhus C 8000, Denmark.
  6. #Instrument Centre for Solid-State NMR Spectroscopy, Department of Chemistry, and Interdisciplinary Nanoscience Center (iNANO), Aarhus University, Langelandsgade 140, Aarhus C 8000, Denmark.

PMID: 26196159 DOI: 10.1021/acs.inorgchem.5b00951

Abstract

Fourteen solvent- and halide-free ammine rare-earth metal borohydrides M(BH4)3·nNH3, M = Y, Gd, Dy, n = 7, 6, 5, 4, 2, and 1, have been synthesized by a new approach, and their structures as well as chemical and physical properties are characterized. Extensive series of coordination complexes with systematic variation in the number of ligands are presented, as prepared by combined mechanochemistry, solvent-based methods, solid-gas reactions, and thermal treatment. This new synthesis approach may have a significant impact within inorganic coordination chemistry. Halide-free metal borohydrides have been synthesized by solvent-based metathesis reactions of LiBH4 and MCl3 (3:1), followed by reactions of M(BH4)3 with an excess of NH3 gas, yielding M(BH4)3·7NH3 (M = Y, Gd, and Dy). Crystal structure models for M(BH4)3·nNH3 are derived from a combination of powder X-ray diffraction (PXD), (11)B magic-angle spinning NMR, and density functional theory (DFT) calculations. The structures vary from two-dimensional layers (n = 1), one-dimensional chains (n = 2), molecular compounds (n = 4 and 5), to contain complex ions (n = 6 and 7). NH3 coordinates to the metal in all compounds, while BH4(-) has a flexible coordination, i.e., either as a terminal or bridging ligand or as a counterion. M(BH4)3·7NH3 releases ammonia stepwise by thermal treatment producing M(BH4)3·nNH3 (6, 5, and 4), whereas hydrogen is released for n ≤ 4. Detailed analysis of the dihydrogen bonds reveals new insight about the hydrogen elimination mechanism, which contradicts current hypotheses. Overall, the present work provides new general knowledge toward rational materials design and preparation along with limitations of PXD and DFT for analysis of structures with a significant degree of dynamics in the structures.

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