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Preferential photostructural modification of heteroleptic titanium alkoxides for molecular assembly

Published online by Cambridge University Press:  31 January 2011

J.D. Musgraves ,
B.G. Potter Jr. ,
Robin M. Sewell  and
Timothy J. Boyle
J.D. Musgraves*
Affiliation:
Materials Science and Engineering Department, University of Arizona, Tucson, Arizona 85721
B.G. Potter Jr.
Affiliation:
Materials Science and Engineering Department, University of Arizona, Tucson, Arizona 85721
Robin M. Sewell
Affiliation:
Sandia National Laboratories, Advanced Materials Laboratory, Albuquerque, New Mexico 87106
Timothy J. Boyle
Affiliation:
Sandia National Laboratories, Advanced Materials Laboratory, Albuquerque, New Mexico 87106
*
a)Address all correspondence to this author. e-mail: [email protected]
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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.

Keywords

Laser-induced reactionPhotochemicalSolution deposition
Type
Articles
Information
Journal of Materials Research , Volume 22 , Issue 6 , June 2007 , pp. 1694 - 1700
Copyright
Copyright © Materials Research Society2007

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References

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