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

Treadwell, LaRico J.; Boyle, Timothy J.; Phelan, W. Adam; Parkes, Marie V.; Young, David P.

doi:10.1039/c6dt04083g

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

Journal Article · Wed Feb 22 00:00:00 EST 2017 · Dalton Transactions

DOI:https://doi.org/10.1039/c6dt04083g· OSTI ID:1360928

Treadwell, LaRico J. ^[1];

^[1]; Phelan, W. Adam ^[2]; Parkes, Marie V. ^[1]; Young, David P. ^[2]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Advanced Materials Lab.
Louisiana State Univ., Baton Rouge, LA (United States). Dept. of Physics and Astronomy

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)μ_B 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.

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Research Organization:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1360928

Report Number(s):: SAND2017-5498J; ICHBD9; 653577

Journal Information:: Dalton Transactions, Vol. 46, Issue 18; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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CCDC 1510806: Experimental Crystal Structure Determination: XARXEW : bis(2-isopropylphenolato)-tetrakis(pyridine)-nickel(ii) Treadwell, LaRico; Boyle, Timothy; Phelan, W. Adam https://doi.org/10.5517/ccdc.csd.cc1mq3p4 The current record is supplemented by this dataset	dataset	October 2016
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Title: Synthesis and characterization of a series of nickel( ii ) alkoxide precursors and their utility for Ni(0) nanoparticle production

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