Preferential photostructural modification of heteroleptic titanium alkoxides for molecular assembly

J. D. Musgraves, Barrett G Potter, Robin M. Sewell, Timothy J. Boyle

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

The response of a mononuclear, heteroleptic titanium alkoxide [(OPy)2Ti(4MP)2, where OPy = pyridinecarbinol; NC5H4(CH2O) and 4MP = 4-mercaptophenol; OC6H4(SH)] to ultraviolet (UV) irradiation in dilute solution and in solid-state samples has been measured. Vibrational spectroscopy [Fourier transform infrared (FTIR) absorption and Raman scattering] was used to monitor changes in molecular structure upon exposure to 337.1- and 365-nm light. Assignment of spectral features to vibrational modes of the molecule was aided by a normal-mode analysis of the energy-minimized molecular structure within a density-functional theory framework. Photoinduced decreases in peak areas were observed in both FTIR spectra of the precursor solutions and Raman data collected from solution-cast films of the precursor material. These changes were associated with vibrational modes localized at the 4MP ligands. Conversely, no significant modification of vibrational structure associated with the OPy moiety was observed under the excitation conditions examined. In a related study, thin films of the precursor were cast, sampled, and irradiated with UV light in scintillation vials under hydrated air (40% relative humidity) and dry Ar to evaluate the influence of local atmospheric composition on the photoresponse. An increase in the magnitude of photoinduced vibrational changes was observed in the moist-air environment, again associated primarily with the 4MP ligand. The results support an interpretation of these structural changes in terms of a preferential enhancement of hydrolysis at the 4MP site under these conditions. These findings are discussed in the context of an optically driven molecular assembly strategy based on the photoinitiation of intermolecular bonding at selected sites about the metal center.

Original languageEnglish (US)
Pages (from-to)1694-1700
Number of pages7
JournalJournal of Materials Research
Volume22
Issue number6
DOIs
StatePublished - Jun 2007

Fingerprint

alkoxides
Titanium
titanium
assembly
Molecular structure
casts
vibration mode
Fourier transforms
molecular structure
Atmospheric composition
Ligands
atmospheric composition
Vibrational spectroscopy
ligands
air
Infrared absorption
Scintillation
Air
ultraviolet radiation
infrared absorption

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

Preferential photostructural modification of heteroleptic titanium alkoxides for molecular assembly. / Musgraves, J. D.; Potter, Barrett G; Sewell, Robin M.; Boyle, Timothy J.

In: Journal of Materials Research, Vol. 22, No. 6, 06.2007, p. 1694-1700.

Research output: Contribution to journalArticle

Musgraves, J. D. ; Potter, Barrett G ; Sewell, Robin M. ; Boyle, Timothy J. / Preferential photostructural modification of heteroleptic titanium alkoxides for molecular assembly. In: Journal of Materials Research. 2007 ; Vol. 22, No. 6. pp. 1694-1700.
@article{7a5505a13647491694f5f67b1b070055,
title = "Preferential photostructural modification of heteroleptic titanium alkoxides for molecular assembly",
abstract = "The response of a mononuclear, heteroleptic titanium alkoxide [(OPy)2Ti(4MP)2, where OPy = pyridinecarbinol; NC5H4(CH2O) and 4MP = 4-mercaptophenol; OC6H4(SH)] to ultraviolet (UV) irradiation in dilute solution and in solid-state samples has been measured. Vibrational spectroscopy [Fourier transform infrared (FTIR) absorption and Raman scattering] was used to monitor changes in molecular structure upon exposure to 337.1- and 365-nm light. Assignment of spectral features to vibrational modes of the molecule was aided by a normal-mode analysis of the energy-minimized molecular structure within a density-functional theory framework. Photoinduced decreases in peak areas were observed in both FTIR spectra of the precursor solutions and Raman data collected from solution-cast films of the precursor material. These changes were associated with vibrational modes localized at the 4MP ligands. Conversely, no significant modification of vibrational structure associated with the OPy moiety was observed under the excitation conditions examined. In a related study, thin films of the precursor were cast, sampled, and irradiated with UV light in scintillation vials under hydrated air (40{\%} relative humidity) and dry Ar to evaluate the influence of local atmospheric composition on the photoresponse. An increase in the magnitude of photoinduced vibrational changes was observed in the moist-air environment, again associated primarily with the 4MP ligand. The results support an interpretation of these structural changes in terms of a preferential enhancement of hydrolysis at the 4MP site under these conditions. These findings are discussed in the context of an optically driven molecular assembly strategy based on the photoinitiation of intermolecular bonding at selected sites about the metal center.",
author = "Musgraves, {J. D.} and Potter, {Barrett G} and Sewell, {Robin M.} and Boyle, {Timothy J.}",
year = "2007",
month = "6",
doi = "10.1557/jmr.2007.0219",
language = "English (US)",
volume = "22",
pages = "1694--1700",
journal = "Journal of Materials Research",
issn = "0884-2914",
publisher = "Materials Research Society",
number = "6",

}

TY - JOUR

T1 - Preferential photostructural modification of heteroleptic titanium alkoxides for molecular assembly

AU - Musgraves, J. D.

AU - Potter, Barrett G

AU - Sewell, Robin M.

AU - Boyle, Timothy J.

PY - 2007/6

Y1 - 2007/6

N2 - The response of a mononuclear, heteroleptic titanium alkoxide [(OPy)2Ti(4MP)2, where OPy = pyridinecarbinol; NC5H4(CH2O) and 4MP = 4-mercaptophenol; OC6H4(SH)] to ultraviolet (UV) irradiation in dilute solution and in solid-state samples has been measured. Vibrational spectroscopy [Fourier transform infrared (FTIR) absorption and Raman scattering] was used to monitor changes in molecular structure upon exposure to 337.1- and 365-nm light. Assignment of spectral features to vibrational modes of the molecule was aided by a normal-mode analysis of the energy-minimized molecular structure within a density-functional theory framework. Photoinduced decreases in peak areas were observed in both FTIR spectra of the precursor solutions and Raman data collected from solution-cast films of the precursor material. These changes were associated with vibrational modes localized at the 4MP ligands. Conversely, no significant modification of vibrational structure associated with the OPy moiety was observed under the excitation conditions examined. In a related study, thin films of the precursor were cast, sampled, and irradiated with UV light in scintillation vials under hydrated air (40% relative humidity) and dry Ar to evaluate the influence of local atmospheric composition on the photoresponse. An increase in the magnitude of photoinduced vibrational changes was observed in the moist-air environment, again associated primarily with the 4MP ligand. The results support an interpretation of these structural changes in terms of a preferential enhancement of hydrolysis at the 4MP site under these conditions. These findings are discussed in the context of an optically driven molecular assembly strategy based on the photoinitiation of intermolecular bonding at selected sites about the metal center.

AB - The response of a mononuclear, heteroleptic titanium alkoxide [(OPy)2Ti(4MP)2, where OPy = pyridinecarbinol; NC5H4(CH2O) and 4MP = 4-mercaptophenol; OC6H4(SH)] to ultraviolet (UV) irradiation in dilute solution and in solid-state samples has been measured. Vibrational spectroscopy [Fourier transform infrared (FTIR) absorption and Raman scattering] was used to monitor changes in molecular structure upon exposure to 337.1- and 365-nm light. Assignment of spectral features to vibrational modes of the molecule was aided by a normal-mode analysis of the energy-minimized molecular structure within a density-functional theory framework. Photoinduced decreases in peak areas were observed in both FTIR spectra of the precursor solutions and Raman data collected from solution-cast films of the precursor material. These changes were associated with vibrational modes localized at the 4MP ligands. Conversely, no significant modification of vibrational structure associated with the OPy moiety was observed under the excitation conditions examined. In a related study, thin films of the precursor were cast, sampled, and irradiated with UV light in scintillation vials under hydrated air (40% relative humidity) and dry Ar to evaluate the influence of local atmospheric composition on the photoresponse. An increase in the magnitude of photoinduced vibrational changes was observed in the moist-air environment, again associated primarily with the 4MP ligand. The results support an interpretation of these structural changes in terms of a preferential enhancement of hydrolysis at the 4MP site under these conditions. These findings are discussed in the context of an optically driven molecular assembly strategy based on the photoinitiation of intermolecular bonding at selected sites about the metal center.

UR - http://www.scopus.com/inward/record.url?scp=34347220817&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=34347220817&partnerID=8YFLogxK

U2 - 10.1557/jmr.2007.0219

DO - 10.1557/jmr.2007.0219

M3 - Article

AN - SCOPUS:34347220817

VL - 22

SP - 1694

EP - 1700

JO - Journal of Materials Research

JF - Journal of Materials Research

SN - 0884-2914

IS - 6

ER -