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 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.more »
- Authors:
-
[1];
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- College of the Holy Cross, Worcester, MA (United States)
- 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}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
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
- Boyle, Timothy J.; Farrell, Joshua; Yonemoto, Daniel T.
- Cambridge Structural Database (CSD)
CCDC 1854169: Experimental Crystal Structure Determination: ZIHZOI : (2,2-dimethylpropan-1-olato)-{2,2'-[{[2-(oxy)ethyl]azanediyl}bis(methylene)]bis(4,6-di-t-butylphenolato)}-titanium(iv)
dataset, July 2018
- Boyle, Timothy J.; Farrell, Joshua; Yonemoto, Daniel T.
- Cambridge Structural Database (CSD)
CCDC 1854170: Experimental Crystal Structure Determination: ZIHZUO : bis(μ-2,2'-[{[2-(oxy)ethyl]azanediyl}bis(methylene)]bis(4,6-di-t-butylphenolato))-bis(propan-2-olato)-di-zirconium(iv) toluene solvate
dataset, July 2018
- Boyle, Timothy J.; Farrell, Joshua; Yonemoto, Daniel T.
- Cambridge Structural Database (CSD)
CCDC 1854171: Experimental Crystal Structure Determination: ZIJBAY : bis(μ-2,2'-[{[2-(oxy)ethyl]azanediyl}bis(methylene)]bis(4,6-di-t-butylphenolato))-bis(2-methylpropan-2-olato)-di-zirconium(iv) toluene solvate
dataset, July 2018
- Boyle, Timothy J.; Farrell, Joshua; Yonemoto, Daniel T.
- Cambridge Structural Database (CSD)
CCDC 1854172: Experimental Crystal Structure Determination: ZIJBEC : bis(μ-2,2'-[{[2-(oxy)ethyl]azanediyl}bis(methylene)]bis(4,6-di-t-butylphenolato))-bis(2,2-dimethylpropan-1-olato)-di-zirconium(iv) toluene solvate
dataset, July 2018
- Boyle, Timothy J.; Farrell, Joshua; Yonemoto, Daniel T.
- Cambridge Structural Database (CSD)
CCDC 1854173: Experimental Crystal Structure Determination: ZIJBIG : bis(μ-2,2'-[{[2-(oxy)ethyl]azanediyl}bis(methylene)]bis(4,6-di-t-butylphenolato))-bis(2-methylpropan-2-olato)-di-hafnium(iv) toluene solvate
dataset, July 2018
- Boyle, Timothy J.; Farrell, Joshua; Yonemoto, Daniel T.
- Cambridge Structural Database (CSD)
CCDC 1854174: Experimental Crystal Structure Determination: ZIJBOM : bis(μ-2,2'-[{[2-(oxy)ethyl]azanediyl}bis(methylene)]bis(4,6-di-t-butylphenolato))-bis(2,2-dimethylpropan-1-olato)-di-hafnium(iv) toluene solvate
dataset, July 2018
- Boyle, Timothy J.; Farrell, Joshua; Yonemoto, Daniel T.
- Cambridge Structural Database (CSD)
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
- Boyle, Timothy J.; Rimsza, Jessica M.; Farrell, Joshua
- Journal of Coordination Chemistry, Vol. 73, Issue 9