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Title: Synthesis, characterization, and utility of trifluoroacetic acid lanthanide precursors for production of varied phase fluorinated lanthanide nanomaterials

Abstract

The synthesis of a series of lanthanide trifluoroacetic acid (H-TFA) derivatives which contain only the TFA and its conjugate acid has been developed. From the reaction of Ln(N(SiMe3)2)3 with an excess amount of H-TFA, the products were identified as: [Ln(μ-TFA)3(H-TFA)2]n (Ln = Y, Ce, Sm, Eu, Gd, Tb, Dy), [Ln(μ-TFA)3(μ-H-TFA)]n·solv (Ln·solv = Pr·2 H-TFA, H3O+, Ho·2py, Er·py, Yb·py, H-TFA), 3[H][(TFA)La(μ-TFA)3La(TFA)(μ-TFA)2(μc-TFA)2]n ½(H2O) ½(H2O, H-TFA) (La·½(H2O) ½(H2O, H-TFA)), [(k2-TFA)Nd(μ-TFA)3]n·H-py+ (Nd·H-py+), [(py)2Tm(μ-TFA)3]n (Tm), or [Lu(μ-TFA)4Lu(μ-TFA)3·H3O+]n (Lu·H3O+). Here, the majority of samples formed long chain polymers with 3 or 4 μ-TFA ligands. Tm was isolated with py coordinated to the metal, whereas Ho, Er, and Yb were isolated with py located within the lattice. Select samples from this set of compounds were used to generate nanomaterials under solvothermal (SOLVO) conditions using pyridine (py) or octylamine at 185 °C for 24 h. The SOLVO products were isolated as: (i) from py: La – fluocerite (LaF3, PDF 98-000-0214, R = 9.64%, 35(0) nm), Tb – terbium fluoride (TbF3, PDF 00-037-1487, R = 4.76%, 21(2) nm), Lu lutetium oxy fluoride (LuOF, PDF 00-052-0779, R = 8.24%, 8(2) nm); (ii) from octylamine: La – fluocerite/lanthanum oxide carbonate (LaF3, PDF 98-000-0214, R = 7.47%, 5(0) nm; La2O2(CO3), PDF 01-070-5539,more » R = 12.32%, 12(0) nm), Tb – terbium oxy fluoride (TbOF, PDF 00-008-0230, R = 7.01%, 5(0) nm); Lu – lutetium oxide (Lu2O3, PDF 00-012-0728, R = 6.52%, 6(1) nm).« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
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  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1871978
Alternate Identifier(s):
OSTI ID: 1398055
Report Number(s):
SAND2022-5358J
Journal ID: ISSN 0277-5387; 705512
Grant/Contract Number:  
NA0003525; AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
Polyhedron
Additional Journal Information:
Journal Volume: 131; Journal ID: ISSN 0277-5387
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Metal carboxylates; Trifluoroacetic acid; TFA; Scintillators; Crystal structure

Citation Formats

Boyle, Timothy J., Yonemoto, Daniel T., Sears, Jeremiah M., Treadwell, LaRico J., Bell, Nelson S., Cramer, Roger E., Neville, Michael L., Stillman, Gregory A. K., and Bingham, Samuel P. Synthesis, characterization, and utility of trifluoroacetic acid lanthanide precursors for production of varied phase fluorinated lanthanide nanomaterials. United States: N. p., 2017. Web. doi:10.1016/j.poly.2017.04.032.
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Boyle, Timothy J., Yonemoto, Daniel T., Sears, Jeremiah M., Treadwell, LaRico J., Bell, Nelson S., Cramer, Roger E., Neville, Michael L., Stillman, Gregory A. K., & Bingham, Samuel P. Synthesis, characterization, and utility of trifluoroacetic acid lanthanide precursors for production of varied phase fluorinated lanthanide nanomaterials. United States. https://doi.org/10.1016/j.poly.2017.04.032
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Boyle, Timothy J., Yonemoto, Daniel T., Sears, Jeremiah M., Treadwell, LaRico J., Bell, Nelson S., Cramer, Roger E., Neville, Michael L., Stillman, Gregory A. K., and Bingham, Samuel P. Wed . "Synthesis, characterization, and utility of trifluoroacetic acid lanthanide precursors for production of varied phase fluorinated lanthanide nanomaterials". United States. https://doi.org/10.1016/j.poly.2017.04.032. https://www.osti.gov/servlets/purl/1871978.
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@article{osti_1871978,
title = {Synthesis, characterization, and utility of trifluoroacetic acid lanthanide precursors for production of varied phase fluorinated lanthanide nanomaterials},
author = {Boyle, Timothy J. and Yonemoto, Daniel T. and Sears, Jeremiah M. and Treadwell, LaRico J. and Bell, Nelson S. and Cramer, Roger E. and Neville, Michael L. and Stillman, Gregory A. K. and Bingham, Samuel P.},
abstractNote = {The synthesis of a series of lanthanide trifluoroacetic acid (H-TFA) derivatives which contain only the TFA and its conjugate acid has been developed. From the reaction of Ln(N(SiMe3)2)3 with an excess amount of H-TFA, the products were identified as: [Ln(μ-TFA)3(H-TFA)2]n (Ln = Y, Ce, Sm, Eu, Gd, Tb, Dy), [Ln(μ-TFA)3(μ-H-TFA)]n·solv (Ln·solv = Pr·2 H-TFA, H3O+, Ho·2py, Er·py, Yb·py, H-TFA), 3[H][(TFA)La(μ-TFA)3La(TFA)(μ-TFA)2(μc-TFA)2]n ½(H2O) ½(H2O, H-TFA) (La·½(H2O) ½(H2O, H-TFA)), [(k2-TFA)Nd(μ-TFA)3]n·H-py+ (Nd·H-py+), [(py)2Tm(μ-TFA)3]n (Tm), or [Lu(μ-TFA)4Lu(μ-TFA)3·H3O+]n (Lu·H3O+). Here, the majority of samples formed long chain polymers with 3 or 4 μ-TFA ligands. Tm was isolated with py coordinated to the metal, whereas Ho, Er, and Yb were isolated with py located within the lattice. Select samples from this set of compounds were used to generate nanomaterials under solvothermal (SOLVO) conditions using pyridine (py) or octylamine at 185 °C for 24 h. The SOLVO products were isolated as: (i) from py: La – fluocerite (LaF3, PDF 98-000-0214, R = 9.64%, 35(0) nm), Tb – terbium fluoride (TbF3, PDF 00-037-1487, R = 4.76%, 21(2) nm), Lu lutetium oxy fluoride (LuOF, PDF 00-052-0779, R = 8.24%, 8(2) nm); (ii) from octylamine: La – fluocerite/lanthanum oxide carbonate (LaF3, PDF 98-000-0214, R = 7.47%, 5(0) nm; La2O2(CO3), PDF 01-070-5539, R = 12.32%, 12(0) nm), Tb – terbium oxy fluoride (TbOF, PDF 00-008-0230, R = 7.01%, 5(0) nm); Lu – lutetium oxide (Lu2O3, PDF 00-012-0728, R = 6.52%, 6(1) nm).},
doi = {10.1016/j.poly.2017.04.032},
journal = {Polyhedron},
number = ,
volume = 131,
place = {United States},
year = {Wed May 10 00:00:00 EDT 2017},
month = {Wed May 10 00:00:00 EDT 2017}
}
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