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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

Abstract

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 H 3-AM-DBP 2 (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(CH 3) 2 (OPr i); OC(CH 3) 3 (OBu t); OCH 2C(CH 3) 3 (ONep) with H 3-AM-DBP 2 proved, by single crystal X-ray diffraction, to be: [(ONep)Ti(k 4(O,O’,O’’,N)-AM-DBP 2)] (2), [(OR)M(μ(O)-k 3(O’,O’’,N)-AM-DBP 2)] 2 [M = Zr: OR = OPr i, 3•tol; OBu t, 4•tol; ONep, 5•tol; M = Hf: OR = OBu t , 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 09more » 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/AMDBP 2 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.« less

Authors:
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)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1473939
Report Number(s):
SAND-2018-10057J
Journal ID: ISSN 0020-1669; 667845
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 17; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Boyle, Timothy J., Farrell, Joshua, Yonemoto, Daniel T., Sears, Jeremiah M., Rimsza, Jessica M., Perales, Diana, Bell, Nelson S., Cramer, Roger E., Treadwell, LaRico J., Renehan, Peter, Adams, Casey J., Bender, Michael T., and Crowley, William. Synthesis, Characterization, and Nanomaterials Generated from 6,6'-(((2-Hydroxyethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol) Modified Group 4 Metal Alkoxides. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.8b01907.
Boyle, Timothy J., Farrell, Joshua, Yonemoto, Daniel T., Sears, Jeremiah M., Rimsza, Jessica M., Perales, Diana, Bell, Nelson S., Cramer, Roger E., Treadwell, LaRico J., Renehan, Peter, Adams, Casey J., Bender, Michael T., & Crowley, William. Synthesis, Characterization, and Nanomaterials Generated from 6,6'-(((2-Hydroxyethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol) Modified Group 4 Metal Alkoxides. United States. doi:10.1021/acs.inorgchem.8b01907.
Boyle, Timothy J., Farrell, Joshua, Yonemoto, Daniel T., Sears, Jeremiah M., Rimsza, Jessica M., Perales, Diana, Bell, Nelson S., Cramer, Roger E., Treadwell, LaRico J., Renehan, Peter, Adams, Casey J., Bender, Michael T., and Crowley, William. Tue . "Synthesis, Characterization, and Nanomaterials Generated from 6,6'-(((2-Hydroxyethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol) Modified Group 4 Metal Alkoxides". United States. doi:10.1021/acs.inorgchem.8b01907. https://www.osti.gov/servlets/purl/1473939.
@article{osti_1473939,
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},
author = {Boyle, Timothy J. and Farrell, Joshua and Yonemoto, Daniel T. and Sears, Jeremiah M. and Rimsza, Jessica M. and Perales, Diana and Bell, Nelson S. and Cramer, Roger E. and Treadwell, LaRico J. and Renehan, Peter and Adams, Casey J. and Bender, Michael T. and Crowley, William},
abstractNote = {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.},
doi = {10.1021/acs.inorgchem.8b01907},
journal = {Inorganic Chemistry},
number = 17,
volume = 57,
place = {United States},
year = {2018},
month = {8}
}

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Works referencing / citing this record:

CCDC 1854168: Experimental Crystal Structure Determination: ZIHZIC : 2,2'-{[(2-hydroxyethyl)azanediyl]bis(methylene)}bis(4,6-di-t-butylphenol)
dataset, July 2018