U.S. Department of Energy Office of Scientific and Technical Information
Synthesis, Characterization, and Nanomaterials Generated from 6,6'-(((2-Hydroxyethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol) Modified Group 4 Metal Alkoxides
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.
Boyle, Timothy J., et al. "Synthesis, Characterization, and Nanomaterials Generated from 6,6'-(((2-Hydroxyethyl)azanediyl)bis(methylene))bis(2,4-di-<i>tert</i>-butylphenol) Modified Group 4 Metal Alkoxides." Inorganic Chemistry, vol. 57, no. 17, Aug. 2018. https://doi.org/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 (2018). Synthesis, Characterization, and Nanomaterials Generated from 6,6'-(((2-Hydroxyethyl)azanediyl)bis(methylene))bis(2,4-di-<i>tert</i>-butylphenol) Modified Group 4 Metal Alkoxides. Inorganic Chemistry, 57(17). https://doi.org/10.1021/acs.inorgchem.8b01907
Boyle, Timothy J., Farrell, Joshua, Yonemoto, Daniel T., et al., "Synthesis, Characterization, and Nanomaterials Generated from 6,6'-(((2-Hydroxyethyl)azanediyl)bis(methylene))bis(2,4-di-<i>tert</i>-butylphenol) Modified Group 4 Metal Alkoxides," Inorganic Chemistry 57, no. 17 (2018), https://doi.org/10.1021/acs.inorgchem.8b01907
@article{osti_1473939,
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 others},
title = {Synthesis, Characterization, and Nanomaterials Generated from 6,6'-(((2-Hydroxyethyl)azanediyl)bis(methylene))bis(2,4-di-<i>tert</i>-butylphenol) Modified Group 4 Metal Alkoxides},
annote = {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},
url = {https://www.osti.gov/biblio/1473939},
journal = {Inorganic Chemistry},
issn = {ISSN 0020-1669},
number = {17},
volume = {57},
place = {United States},
publisher = {American Chemical Society (ACS)},
year = {2018},
month = {08}}