New TiO2 precursor for TiO2:poly(N-vinylcarbazole) (PVK) thin film: Synthesis and reactivity to hydrolysis of titanium tetrakis (9H-carbazole-9-yl-ethyl-oxy)

• Published in: Journal of non-crystalline solids Vol. 355; no. 6; pp. 386 - 392
• Main Authors: Barlier, V., Léonard, D., Boiteux, G., Davenas, J., Boisson, F., Bounor-Legaré, V.
• Format: Journal Article
• Language: English
• Published: Oxford Elsevier B.V 01-03-2009; Elsevier
• Subjects: Chemical Sciences; Cross-disciplinary physics: materials science; rheology; Exact sciences and technology; Materials science; Materials synthesis; materials processing; NMR, MAS-NMR and NQR; Physics; Polymers; Sol–gel, aerogel and solution chemistry; Transition metals; NMR, MAS-NMR and NQR; 68.37.Ps; Transition metals; 81.07.St; 68.37.Xy; Sol–gel, aerogel and solution chemistry; Atomic force microscopy; Alkoxides; MAS-NMR and NQR; Sol-gel; Precursor; Thin films; Hydrolysis; 81.07.St; 68.37.Ps; 68.37.Xy; Transition metals; NMR; aerogel and solution chemistry; Nuclear quadrupole resonance; Nuclear magnetic resonance; Titanium compounds; Microstructure; Chemical reactivity; Chemical synthesis; Sol-gel process; Growth from solution; X-ray photoelectron spectra
• ISSN: 0022-3093; 1873-4812
• DOI: 10.1016/j.jnoncrysol.2008.12.007

The chemical reactivity of the ligand initially coordinated on the TiO2 precursor plays a decisive role in the morphology of TiO2:poly(N-vinylcarbazole) (PVK) thin film elaborated by in situ generation of the inorganic phase in the polymer matrix. The final aim of this study is to prepare a new nanocomposite TiO2:poly(N-vinylcarbazole) (PVK) thin film from hydrolysis-condensation of titanium alkoxide in polymer thin film. In this context, we synthesized a new TiO2 precursor, the tetrakis (9H-carbazole-9-yl-ethyl-oxy) [Ti(OeCarb)4], bearing ligands close to the repetitive unit structure of the PVK to improve the interaction between both materials. In this study, the synthesis and reactivity to hydrolysis of Ti(OeCarb)4 is presented. Ti(OeCarb)4 was elaborated from alcoholysis reaction between titanium isopropoxide [Ti(iOPr)4] and 9H-carbazole-9-ethanol (ECOH) and identified by 1H and 13C NMR spectroscopy. The reactivity to hydrolysis-oxolation of Ti(OeCarb)4 was evaluated first in aqueous media by in situ 1H NMR spectroscopy analysis. Moreover, reactivity of Ti(OeCarb)4 to surrounding humidity was evaluated in thin film by X-ray photoelectron spectroscopy (XPS). Results show that steric hindrance of 9H-carbazole-9-yl-ethyl-oxide ligands do not influence the hydrolysis-condensation process in aqueous media in our experimental conditions when compared to [Ti(iOPr)4] but decrease the reactivity when the precursor is simply exposed to air humidity.