Implications for the thin-film densification of TiO2 from carboxylic acid-modified titanium alkoxides. Syntheses, characterizations, and X-ray structures of various carboxylic acid modified titanium alkoxides (see abstract)

Timothy J. Boyle, Ryan P. Tyner, Todd M. Alam, Brian L. Scott, Joseph W. Ziller, Barrett G Potter

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Abstract

Carboxylic acid (HORc)-modified Ti(OR)4 products were used to study the effect that similarly ligated species with substantially varied structures have on the final densification of the resultant ceramic (in this case TiO2). The 1:1 stoichiometric products isolated from the reactions of [Ti(μ-ONep)(ONep)3]2 (1, ONep = OCH2CMe3) and a variety of sterically hindered carboxylic acids [HORc: HOFc (HO2CH), HOAc (HO2CCH3), HOPc (HO2CCHMe2), HOBc (HO2CCHMe3), or HONc (HO2CCHCMe3)] were identified by single-crystal X-ray diffraction and solid-state 13C MAS NMR spectroscopy as Ti33-O)(OFc)2(ONep)8 (2), Ti33O)(OAc)2(ONep)8 (3), Ti6(μ3- O)6(OPc)6(ONep)6 (4), Ti2(μ-OBc)2(ONep)6 (5), and Ti3(μ3- O)(ONc)2(ONep)8 (6). Compounds 2, 3, and 6 adopt a triangular arrangement of Ti atoms linked by a μ3-oxide moiety with ORc and ONep ligands supporting the basic framework. Compound 4 adopts a distorted, hexagon-prism geometry of two offset [Ti-O-]3 rings with each six-coordinated metal possessing a terminal ONep and two monodentate OPc ligands. The unique, nonesterified product 5 is dimeric with two μ-ONep, two unidentate bridging OBc, and two terminal ONep ligands. The solution behaviors of 2-6 were investigated by NMR experiments and were found to retain the solid-state structure in solution with a great deal of ligand rearrangement. Films of TiO2 were made from redissolved crystals of 2-6. The highest density TiO2 thin films were derived from the partially hydrolyzed, trinuclear, low-carbon-containing ONep complexes 2 and 3, as determined from ellipsometric data.

Original languageEnglish (US)
Pages (from-to)12104-12112
Number of pages9
JournalJournal of the American Chemical Society
Volume121
Issue number51
DOIs
StatePublished - Dec 29 1999
Externally publishedYes

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Carboxylic Acids
Titanium
Carboxylic acids
Densification
Ligands
X-Rays
X rays
Thin films
Ceramics
Prisms
X-Ray Diffraction
Oxides
Nuclear magnetic resonance spectroscopy
Magnetic Resonance Spectroscopy
Carbon
Metals
Nuclear magnetic resonance
Single crystals
X ray diffraction
Atoms

ASJC Scopus subject areas

  • Chemistry(all)

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Implications for the thin-film densification of TiO2 from carboxylic acid-modified titanium alkoxides. Syntheses, characterizations, and X-ray structures of various carboxylic acid modified titanium alkoxides (see abstract). / Boyle, Timothy J.; Tyner, Ryan P.; Alam, Todd M.; Scott, Brian L.; Ziller, Joseph W.; Potter, Barrett G.

In: Journal of the American Chemical Society, Vol. 121, No. 51, 29.12.1999, p. 12104-12112.

Research output: Contribution to journalArticle

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title = "Implications for the thin-film densification of TiO2 from carboxylic acid-modified titanium alkoxides. Syntheses, characterizations, and X-ray structures of various carboxylic acid modified titanium alkoxides (see abstract)",
abstract = "Carboxylic acid (HORc)-modified Ti(OR)4 products were used to study the effect that similarly ligated species with substantially varied structures have on the final densification of the resultant ceramic (in this case TiO2). The 1:1 stoichiometric products isolated from the reactions of [Ti(μ-ONep)(ONep)3]2 (1, ONep = OCH2CMe3) and a variety of sterically hindered carboxylic acids [HORc: HOFc (HO2CH), HOAc (HO2CCH3), HOPc (HO2CCHMe2), HOBc (HO2CCHMe3), or HONc (HO2CCHCMe3)] were identified by single-crystal X-ray diffraction and solid-state 13C MAS NMR spectroscopy as Ti3(μ3-O)(OFc)2(ONep)8 (2), Ti3(μ3O)(OAc)2(ONep)8 (3), Ti6(μ3- O)6(OPc)6(ONep)6 (4), Ti2(μ-OBc)2(ONep)6 (5), and Ti3(μ3- O)(ONc)2(ONep)8 (6). Compounds 2, 3, and 6 adopt a triangular arrangement of Ti atoms linked by a μ3-oxide moiety with ORc and ONep ligands supporting the basic framework. Compound 4 adopts a distorted, hexagon-prism geometry of two offset [Ti-O-]3 rings with each six-coordinated metal possessing a terminal ONep and two monodentate OPc ligands. The unique, nonesterified product 5 is dimeric with two μ-ONep, two unidentate bridging OBc, and two terminal ONep ligands. The solution behaviors of 2-6 were investigated by NMR experiments and were found to retain the solid-state structure in solution with a great deal of ligand rearrangement. Films of TiO2 were made from redissolved crystals of 2-6. The highest density TiO2 thin films were derived from the partially hydrolyzed, trinuclear, low-carbon-containing ONep complexes 2 and 3, as determined from ellipsometric data.",
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T1 - Implications for the thin-film densification of TiO2 from carboxylic acid-modified titanium alkoxides. Syntheses, characterizations, and X-ray structures of various carboxylic acid modified titanium alkoxides (see abstract)

AU - Boyle, Timothy J.

AU - Tyner, Ryan P.

AU - Alam, Todd M.

AU - Scott, Brian L.

AU - Ziller, Joseph W.

AU - Potter, Barrett G

PY - 1999/12/29

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N2 - Carboxylic acid (HORc)-modified Ti(OR)4 products were used to study the effect that similarly ligated species with substantially varied structures have on the final densification of the resultant ceramic (in this case TiO2). The 1:1 stoichiometric products isolated from the reactions of [Ti(μ-ONep)(ONep)3]2 (1, ONep = OCH2CMe3) and a variety of sterically hindered carboxylic acids [HORc: HOFc (HO2CH), HOAc (HO2CCH3), HOPc (HO2CCHMe2), HOBc (HO2CCHMe3), or HONc (HO2CCHCMe3)] were identified by single-crystal X-ray diffraction and solid-state 13C MAS NMR spectroscopy as Ti3(μ3-O)(OFc)2(ONep)8 (2), Ti3(μ3O)(OAc)2(ONep)8 (3), Ti6(μ3- O)6(OPc)6(ONep)6 (4), Ti2(μ-OBc)2(ONep)6 (5), and Ti3(μ3- O)(ONc)2(ONep)8 (6). Compounds 2, 3, and 6 adopt a triangular arrangement of Ti atoms linked by a μ3-oxide moiety with ORc and ONep ligands supporting the basic framework. Compound 4 adopts a distorted, hexagon-prism geometry of two offset [Ti-O-]3 rings with each six-coordinated metal possessing a terminal ONep and two monodentate OPc ligands. The unique, nonesterified product 5 is dimeric with two μ-ONep, two unidentate bridging OBc, and two terminal ONep ligands. The solution behaviors of 2-6 were investigated by NMR experiments and were found to retain the solid-state structure in solution with a great deal of ligand rearrangement. Films of TiO2 were made from redissolved crystals of 2-6. The highest density TiO2 thin films were derived from the partially hydrolyzed, trinuclear, low-carbon-containing ONep complexes 2 and 3, as determined from ellipsometric data.

AB - Carboxylic acid (HORc)-modified Ti(OR)4 products were used to study the effect that similarly ligated species with substantially varied structures have on the final densification of the resultant ceramic (in this case TiO2). The 1:1 stoichiometric products isolated from the reactions of [Ti(μ-ONep)(ONep)3]2 (1, ONep = OCH2CMe3) and a variety of sterically hindered carboxylic acids [HORc: HOFc (HO2CH), HOAc (HO2CCH3), HOPc (HO2CCHMe2), HOBc (HO2CCHMe3), or HONc (HO2CCHCMe3)] were identified by single-crystal X-ray diffraction and solid-state 13C MAS NMR spectroscopy as Ti3(μ3-O)(OFc)2(ONep)8 (2), Ti3(μ3O)(OAc)2(ONep)8 (3), Ti6(μ3- O)6(OPc)6(ONep)6 (4), Ti2(μ-OBc)2(ONep)6 (5), and Ti3(μ3- O)(ONc)2(ONep)8 (6). Compounds 2, 3, and 6 adopt a triangular arrangement of Ti atoms linked by a μ3-oxide moiety with ORc and ONep ligands supporting the basic framework. Compound 4 adopts a distorted, hexagon-prism geometry of two offset [Ti-O-]3 rings with each six-coordinated metal possessing a terminal ONep and two monodentate OPc ligands. The unique, nonesterified product 5 is dimeric with two μ-ONep, two unidentate bridging OBc, and two terminal ONep ligands. The solution behaviors of 2-6 were investigated by NMR experiments and were found to retain the solid-state structure in solution with a great deal of ligand rearrangement. Films of TiO2 were made from redissolved crystals of 2-6. The highest density TiO2 thin films were derived from the partially hydrolyzed, trinuclear, low-carbon-containing ONep complexes 2 and 3, as determined from ellipsometric data.

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