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Title: Alkali metal yttrium neo-pentoxide double alkoxide precursors to alkali metal yttrium oxide nanomaterials

Abstract

In this study, a series of alkali metal yttrium neo-pentoxide ([AY(ONep) 4]) compounds were developed as precursors to alkali yttrium oxide (AYO 2) nanomaterials. The reaction of yttrium amide ([Y(NR 2) 3] where R=Si(CH 3) 3) with four equivalents of H-ONep followed by addition of [A(NR 2)] (A=Li, Na, K) or A o (A o=Rb, Cs) led to the formation of a complex series of A nY(ONep) 3+n species, crystallographically identified as [Y 2Li 33-ONep)(μ 3-HONep)(μ-ONep) 5(ONep) 3(HONep) 2] (1), [YNa 23-ONep) 4(ONep)] 2 (2), {[Y 2K 33-ONep) 3(μ-ONep) 4(ONep) 2(ηξ-tol) 2][Y 4K 24-O)(μ 3-ONep) 8(ONep) 4]•η x-tol]} (3), [Y 4K 24-O)(μ 3-ONep) 8(ONep) 4] (3a), [Y 2Rb 34-ONep) 3(μ-ONep) 6] (4), and [Y 2Cs 46-O)(μ 3-ONep) 63-HONep) 2(ONep) 2x-tol) 4]•tol (5). Compounds 1–5 were investigated as single source precursors to AYOx nanomaterials following solvothermal routes (pyridine, 185 °C for 24h). The final products after thermal processing were found by powder X-ray diffraction experiments to be Y 2O 3 with variable sized particles based on transmission electron diffraction. Energy dispersive X-ray spectroscopy studies indicated that the heavier alkali metal species were present in the isolated nanomaterials.

Authors:
 [1];  [1];  [1];  [2]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. Univ. of Hawaii, Honolulu, HI (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:
1249092
Report Number(s):
SAND-2016-1744J
Journal ID: ISSN 2365-6549; 619560
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry Select
Additional Journal Information:
Journal Volume: 1; Journal Issue: 3; Journal ID: ISSN 2365-6549
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alkoxides; yttrium; alkali metal; neo-pentoxide; nanomaterials

Citation Formats

Boyle, Timothy J., Neville, Michael L., Sears, Jeremiah Matthew, and Cramer, Roger. Alkali metal yttrium neo-pentoxide double alkoxide precursors to alkali metal yttrium oxide nanomaterials. United States: N. p., 2016. Web. doi:10.1002/slct.201600138.
Boyle, Timothy J., Neville, Michael L., Sears, Jeremiah Matthew, & Cramer, Roger. Alkali metal yttrium neo-pentoxide double alkoxide precursors to alkali metal yttrium oxide nanomaterials. United States. doi:10.1002/slct.201600138.
Boyle, Timothy J., Neville, Michael L., Sears, Jeremiah Matthew, and Cramer, Roger. Tue . "Alkali metal yttrium neo-pentoxide double alkoxide precursors to alkali metal yttrium oxide nanomaterials". United States. doi:10.1002/slct.201600138. https://www.osti.gov/servlets/purl/1249092.
@article{osti_1249092,
title = {Alkali metal yttrium neo-pentoxide double alkoxide precursors to alkali metal yttrium oxide nanomaterials},
author = {Boyle, Timothy J. and Neville, Michael L. and Sears, Jeremiah Matthew and Cramer, Roger},
abstractNote = {In this study, a series of alkali metal yttrium neo-pentoxide ([AY(ONep)4]) compounds were developed as precursors to alkali yttrium oxide (AYO2) nanomaterials. The reaction of yttrium amide ([Y(NR2)3] where R=Si(CH3)3) with four equivalents of H-ONep followed by addition of [A(NR2)] (A=Li, Na, K) or Ao (Ao=Rb, Cs) led to the formation of a complex series of AnY(ONep)3+n species, crystallographically identified as [Y2Li3(μ3-ONep)(μ3-HONep)(μ-ONep)5(ONep)3(HONep)2] (1), [YNa2(μ3-ONep)4(ONep)]2 (2), {[Y2K3(μ3-ONep)3(μ-ONep)4(ONep)2(ηξ-tol)2][Y4K2(μ4-O)(μ3-ONep)8(ONep)4]•ηx-tol]} (3), [Y4K2(μ4-O)(μ3-ONep)8(ONep)4] (3a), [Y2Rb3(μ4-ONep)3(μ-ONep)6] (4), and [Y2Cs4(μ6-O)(μ3-ONep)6(μ3-HONep)2(ONep)2(ηx-tol)4]•tol (5). Compounds 1–5 were investigated as single source precursors to AYOx nanomaterials following solvothermal routes (pyridine, 185 °C for 24h). The final products after thermal processing were found by powder X-ray diffraction experiments to be Y2O3 with variable sized particles based on transmission electron diffraction. Energy dispersive X-ray spectroscopy studies indicated that the heavier alkali metal species were present in the isolated nanomaterials.},
doi = {10.1002/slct.201600138},
journal = {Chemistry Select},
issn = {2365-6549},
number = 3,
volume = 1,
place = {United States},
year = {2016},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Figures / Tables:

Table 1. Table 1.: Data collection parameters for 1 - 5.

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Works referenced in this record:

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    journal, September 2003

    • Klinkhammer, Karl W.; Klett, Jan; Xiong, Yun
    • European Journal of Inorganic Chemistry, Vol. 2003, Issue 18
    • DOI: 10.1002/ejic.200300416

    Heterobimetallic Rare Earth-Lithium Complexes with Fewer Than Three Binaphtholates
    journal, April 2013

    • Sircoglou, Marie; Yang, Jing; Guillot, Régis
    • European Journal of Inorganic Chemistry, Vol. 2013, Issue 15
    • DOI: 10.1002/ejic.201300201

    Yttrium containing head-on complexes of silico- and germanotungstate: Synthesis, structure and solution properties
    journal, December 2010

    • Hussain, Firasat; Degonda, Alois; Sandriesser, Stefan
    • Inorganica Chimica Acta, Vol. 363, Issue 15
    • DOI: 10.1016/j.ica.2010.07.053

    Synthesis and characterization of a family of solvated sodium aryloxide compounds
    journal, August 2013

    • Boyle, Timothy J.; Velazquez, Andrew T.; Yonemoto, Daniel T.
    • Inorganica Chimica Acta, Vol. 405
    • DOI: 10.1016/j.ica.2013.06.015

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    journal, September 2004


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    • DOI: 10.1021/ic0106569

    Synthesis and Characterization of a Series of Rubidium Alkoxides and Rubidium−Titanium Double Alkoxides
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    • Bunge, Scott D.; Boyle, Timothy J.; Pratt, Harry D.
    • Inorganic Chemistry, Vol. 43, Issue 19
    • DOI: 10.1021/ic049325x

    Speciation in the AlCl 3 /SO 2 Cl 2 Catholyte System
    journal, August 2005

    • Boyle, Timothy J.; Andrews, Nicholas L.; Alam, Todd M.
    • Inorganic Chemistry, Vol. 44, Issue 16
    • DOI: 10.1021/ic050621z

    Isostructural neo -Pentoxide Derivatives of Group 3 and the Lanthanide Series Metals for the Production of Ln 2 O 3 Nanoparticles
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    • Inorganic Chemistry, Vol. 46, Issue 9
    • DOI: 10.1021/ic070253u

    Structural Diversity in a Series of Alkyl-Substituted Cesium Aryloxides
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    • Boyle, Timothy J.; Steele, Leigh Anna M.; Saad, Alia M.
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    • DOI: 10.1021/ic201438s

    Peculiar Binding Modes of a Ligand with Two Adjacent β-Diiminato Binding Sites in Alkali and Alkaline-Earth Metal Chemistry
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    • DOI: 10.1021/ja7107933

    Optical Limiting in Organic Molecular Nano/Microcrystals: Nonlinear Optical Effects Dependent on Size Distribution
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    • Patra, A.; Venkatram, N.; Rao, D. Narayana
    • The Journal of Physical Chemistry C, Vol. 112, Issue 42
    • DOI: 10.1021/jp803724e

    Upconversion Nanoparticle-Based FRET System for Study of siRNA in Live Cells
    journal, May 2010


    Ultrasmall Monodisperse NaYF4:Yb3+/Tm3+ Nanocrystals with Enhanced Near-Infrared to Near-Infrared Upconversion Photoluminescence
    journal, May 2010

    • Chen, Guanying; Ohulchanskyy, Tymish Y.; Kumar, Rajiv
    • ACS Nano, Vol. 4, Issue 6, p. 3163-3168
    • DOI: 10.1021/nn100457j

    Pinwheel-Shaped Heterobimetallic Lanthanide Alkali Metal Binaphtholates:  Ionic Size Matters!
    journal, December 2000

    • Aspinall, Helen C.; Bickley, Jamie F.; Dwyer, Jennifer L. M.
    • Organometallics, Vol. 19, Issue 25
    • DOI: 10.1021/om0006256

    Li 3 [Ln(binol) 3 ]·6THF:  New Anhydrous Lithium Lanthanide Binaphtholates and Their Use in Enantioselective Alkyl Addition to Aldehydes
    journal, April 1999

    • Aspinall, Helen C.; Dwyer, Jennifer L. M.; Greeves, Nicholas
    • Organometallics, Vol. 18, Issue 8
    • DOI: 10.1021/om981011s

    Magnetic relaxation pathways in lanthanide single-molecule magnets
    journal, July 2013

    • Blagg, Robin J.; Ungur, Liviu; Tuna, Floriana
    • Nature Chemistry, Vol. 5, Issue 8
    • DOI: 10.1038/nchem.1707

    Synthesis and structure of arene soluble N,N′-bis(di-tert-butylsalicylidene)ethylenediamine yttrium complexes
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    • Evans, William J.; Fujimoto, Cy H.; Ziller, Joseph W.
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    • DOI: 10.1039/a807470d

    Rare earth fluoride nano-/microcrystals: synthesis, surface modification and application
    journal, January 2010

    • Li, Chunxia; Lin, Jun
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    • DOI: 10.1039/c0jm00031k

    Low co-ordination numbers in lanthanide and actinide compounds. Part I. The preparation and characterization of tris{bis(trimethylsilyl)-amido}lanthanides
    journal, January 1973

    • Bradley, Donald C.; Ghotra, Joginder S.; Hart, F. Alan
    • Journal of the Chemical Society, Dalton Transactions, Issue 10
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    Synthesis and characterization of a series of rubidium aryloxide compounds
    journal, April 2013

    • Boyle, Timothy J.; Velazquez, Andrew T.; Yonemoto, Daniel T.
    • Journal of Coordination Chemistry, Vol. 66, Issue 7
    • DOI: 10.1080/00958972.2013.777435

      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.