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Title: Synthesis and characterization of a series of nickel( ii ) alkoxide precursors and their utility for Ni(0) nanoparticle production

We synthesized a series of nickel(II) aryloxide ([Ni(OAr) 2(py) x]) precursors from an amide-alcohol exchange using [Ni(NR 2) 2] in the presence of pyridine (py). The H-OAr selected were the mono- and di-ortho-substituted 2-alkyl phenols: alkyl = methyl (H-oMP), iso-propyl (H-oPP), tert-butyl (H-oBP) and 2,6-di-alkyl phenols (alkyl = di-iso-propyl (H-DIP), di-tert-butyl (H-DBP), di-phenyl (H-DPhP)). Furthermore, the crystalline products were solved as solvated monomers and structurally characterized as [Ni(OAr) 2(py) x], where x = 4: OAr = oMP (1), oPP (2); x = 3: OAr = oBP (3), DIP (4); x = 2: OAr = DBP (5), DPhP (6). The excited states (singlet or triplet) and various geometries of 1–6 were identified by experimental UV-vis and verified by computational modeling. Magnetic susceptibility of the representative compound 4 was fit to a Curie Weiss model that yielded a magnetic moment of 4.38(3)μ B consistent with a Ni 2+ center. Compounds 1 and 6 were selected for decomposition studied under solution precipitation routes since they represent the two extremes of coordination. The particle size and crystalline structure were characterized using transmission electron microscopy (TEM) and powder X-ray diffraction (PXRD). Finally, the materials isolated from 1 and 6 were found by TEM to formmore » irregular shape nanomaterials (8–15 nm), which by PXRD were found to be Ni 0 hcp (PDF: 01-089-7129) and fcc (PDF: 01-070-0989), respectively.« less
Authors:
 [1] ; ORCiD logo [1] ;  [2] ;  [1] ;  [2]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Advanced Materials Lab.
  2. Louisiana State Univ., Baton Rouge, LA (United States). Dept. of Physics and Astronomy
Publication Date:
Report Number(s):
SAND2017-5498J
Journal ID: ISSN 1477-9226; ICHBD9; 653577
Grant/Contract Number:
AC04-94AL85000
Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 46; Journal Issue: 18; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Research Org:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
OSTI Identifier:
1360928

Treadwell, LaRico J., Boyle, Timothy J., Phelan, W. Adam, Parkes, Marie V., and Young, David P.. Synthesis and characterization of a series of nickel( ii ) alkoxide precursors and their utility for Ni(0) nanoparticle production. United States: N. p., Web. doi:10.1039/c6dt04083g.
Treadwell, LaRico J., Boyle, Timothy J., Phelan, W. Adam, Parkes, Marie V., & Young, David P.. Synthesis and characterization of a series of nickel( ii ) alkoxide precursors and their utility for Ni(0) nanoparticle production. United States. doi:10.1039/c6dt04083g.
Treadwell, LaRico J., Boyle, Timothy J., Phelan, W. Adam, Parkes, Marie V., and Young, David P.. 2017. "Synthesis and characterization of a series of nickel( ii ) alkoxide precursors and their utility for Ni(0) nanoparticle production". United States. doi:10.1039/c6dt04083g. https://www.osti.gov/servlets/purl/1360928.
@article{osti_1360928,
title = {Synthesis and characterization of a series of nickel( ii ) alkoxide precursors and their utility for Ni(0) nanoparticle production},
author = {Treadwell, LaRico J. and Boyle, Timothy J. and Phelan, W. Adam and Parkes, Marie V. and Young, David P.},
abstractNote = {We synthesized a series of nickel(II) aryloxide ([Ni(OAr)2(py)x]) precursors from an amide-alcohol exchange using [Ni(NR2)2] in the presence of pyridine (py). The H-OAr selected were the mono- and di-ortho-substituted 2-alkyl phenols: alkyl = methyl (H-oMP), iso-propyl (H-oPP), tert-butyl (H-oBP) and 2,6-di-alkyl phenols (alkyl = di-iso-propyl (H-DIP), di-tert-butyl (H-DBP), di-phenyl (H-DPhP)). Furthermore, the crystalline products were solved as solvated monomers and structurally characterized as [Ni(OAr)2(py)x], where x = 4: OAr = oMP (1), oPP (2); x = 3: OAr = oBP (3), DIP (4); x = 2: OAr = DBP (5), DPhP (6). The excited states (singlet or triplet) and various geometries of 1–6 were identified by experimental UV-vis and verified by computational modeling. Magnetic susceptibility of the representative compound 4 was fit to a Curie Weiss model that yielded a magnetic moment of 4.38(3)μB consistent with a Ni2+ center. Compounds 1 and 6 were selected for decomposition studied under solution precipitation routes since they represent the two extremes of coordination. The particle size and crystalline structure were characterized using transmission electron microscopy (TEM) and powder X-ray diffraction (PXRD). Finally, the materials isolated from 1 and 6 were found by TEM to form irregular shape nanomaterials (8–15 nm), which by PXRD were found to be Ni0 hcp (PDF: 01-089-7129) and fcc (PDF: 01-070-0989), respectively.},
doi = {10.1039/c6dt04083g},
journal = {Dalton Transactions},
number = 18,
volume = 46,
place = {United States},
year = {2017},
month = {2}
}

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