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DFT modeling, UV-Vis and IR spectroscopic study of acetylacetone-modified zirconia sol-gel materials

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Abstract

Theoretical and spectroscopic studies of a series of monomeric and dimeric complexes formed through the modification of a zirconium butoxide precursor with acetylacetone and subsequent hydrolysis and/or condensation have been performed by applying DFT/B3LYP/6-31++G(d) and highly accurate RI-ADC(2) methods as well as IR and UV-Vis transmittance and diffuse reflectance spectroscopies. Based on DFT model calculations and simulated and experimental UV-Vis and IR spectra of all the studied structures, the most probable building units of the Zr(IV)–AcAc gel were predicted: the dimeric double hydroxo-bridged complex Zr2(AcAc)2(OH)4(OH)2br 9 and the monooxo-bridged complex Zr2(AcAc)2(OH)4Obr·2H2O 12. In both structures, the two AcAc ligands are coordinated to one Zr atom. It was shown that building units 9 and 12 determine the photophysical and vibrational properties of the gel material. The observed UV-Vis and IR spectra of Zr(IV)-AcAc gel were interpreted and a relation between the spectroscopic and structural data was derived. The observed UV-Vis bands at 315 nm and 298/288 nm were assigned to partial ligand–metal transitions and to intra-/inter-AcAc ligand transitions, respectively.

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Acknowledgments

The authors thank the National Science Fund of Bulgaria (NSFB) under grants DO-02-233/2008 and DCVP-02/2/2009. S.G. and N.D. were supported by grant TK 02-26/2009 from the NSFB. All computations were performed on the MADARA cluster of the Bulgarian Academy of Sciences.

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Authors and Affiliations

  1. Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 11 Acad. G. Bonchev Str., 1113, Sofia, Bulgaria

    Ivelina Georgieva & Natasha Trendafilova

  2. Department of Physical Chemistry, University of Sofia “St. Kliment Ohridski”, James Bourchier Boulevard 1, 1164, Sofia, Bulgaria

    Nina Danchova & Stoyan Gutzov

Authors
  1. Ivelina Georgieva
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  2. Nina Danchova
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  3. Stoyan Gutzov
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  4. Natasha Trendafilova
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Corresponding author

Correspondence to Ivelina Georgieva.

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Georgieva, I., Danchova, N., Gutzov, S. et al. DFT modeling, UV-Vis and IR spectroscopic study of acetylacetone-modified zirconia sol-gel materials. J Mol Model 18, 2409–2422 (2012). https://doi.org/10.1007/s00894-011-1257-3

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  • DOI: https://doi.org/10.1007/s00894-011-1257-3

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