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Title: Synthesis, Characterization, and Nanomaterials Generated from 6,6'-(((2-Hydroxyethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol) Modified Group 4 Metal Alkoxides

Journal Article · · Inorganic Chemistry
ORCiD logo [1];  [2];  [1];  [1];  [1];  [1];  [1];  [3];  [1];  [2];  [1];  [1];  [2]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. College of the Holy Cross, Worcester, MA (United States)
  3. Univ. of Hawaii, Manoa, HI (United States)
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The impact on the morphology nanoceramic materials generated from group 4 metal alkoxides ([M(OR)4]) and the same precursors modified by 6,6'-(((2- hydroxyethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol) (referred to as H3-AM-DBP2 (1)) was explored. The products isolated from the 1:1 stoichiometric reaction of a series of [M(OR)4] where M= Ti, Zr, or Hf; OR = OCH(CH3)2 (OPri); OC(CH3)3 (OBut); OCH2C(CH3)3 (ONep) with H3-AM-DBP2 proved, by single crystal X-ray diffraction, to be: [(ONep)Ti(k4(O,O’,O’’,N)-AM-DBP2)] (2), [(OR)M(μ(O)-k3(O’,O’’,N)-AM-DBP2)]2 [M = Zr: OR = OPri, 3•tol; OBut, 4•tol; ONep, 5•tol; M = Hf: OR = OBut , 6•tol; ONep, 7•tol]. The product from each system led to a tetradentate AM-DBP2 ligand and retention of a parent alkoxide ligand. For the monomeric Ti derivative (2), the metal was solved in a trigonal bipyramidal geometry; whereas, for the Zr (3 - 5) and Hf (6, 7) derivatives, a symmetric dinuclear complex was formed where the ethoxide moiety of the AM-DBP2 ligand bridges to the other metal center, generating an octahedral geometry. High quality Density Functional Theory level gas-phase electronic structure calculations on compounds 2 - 7 using Gaussian 09 were used for meaningful Time Dependent Density Functional Theory calculations in the interpretation of the UV-vis absorbance spectral data on 2 - 7. Nanoparticles generated from the solvothermal treatment of the ONep/AMDBP2 modified compounds (2, 5, 7) in comparison to their parent [M(ONep)4] were larger, and had improved regularity and dispersion of the final ceramic nanomaterials.

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:
1473939
Report Number(s):
SAND-2018-10057J; 667845
Journal Information:
Inorganic Chemistry, Vol. 57, Issue 17; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

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Cited By (3)

Synthesis, characterization, and computational modeling of 6,6'-(((2-hydroxyethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol) modified group 4 metal alkoxides journal May 2020
Synthesis, characterization, and computational modeling of 6,6'-(((2-hydroxyethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol) modified group 4 metal alkoxides text January 2020
Synthesis, characterization, and computational modeling of 6,6'-(((2-hydroxyethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol) modified group 4 metal alkoxides text January 2020

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