title: DFT study of Raman spectra of phosphorus-containing dendrons built from cyclotriphosphazene core with terminal carbamate and ester groups.
abstract: The FT Raman spectra of the zero (Gv0) and first generations (Gv1) of phosphorus-containing dendrons with terminal carbamate groups and one ester function and [2-(4-hydroxyphenyl)ethyl]-carbamic acid tert-butyl ester (C) have been recorded and analyzed. The lines of free ν(C=O) bonds are not observed in the experimental Raman spectrum of C and thus association of carbamate groups by hydrogen bonds occur. The frequencies of ν(C=O) lines in the experimental Raman spectrum reveal the presence of the different types of H-bonds in the amorphous state of Gv0. Density functional theory (DFT) calculations of C gave geometrical parameters for the t-g-, g-g-, tg-, gg-conformers. The most stable is the gg-conformer. The structural optimization and normal mode analysis were performed for dendrons on the basis of the DFT. The calculated geometrical parameters, harmonic vibrational frequencies and Raman intensities are predicted in a good agreement with the experimental data. The experimental Raman spectra of dendrons were interpreted by means of potential energy distribution. Relying on DFT calculations the lines of a core, repeating units and terminal groups of dendrons were assigned. The polarizabilities and lipophilicity of dendrons were estimated.
authors.affiliation: Kazan State Architect and Civil Engineering University, Zelenaya, 1, 420043 Kazan, Russia. Electronic address: furer@ksaba.ru.
authors.forename: V L
authors.initials: VL
authors.lastname: Furer
authors.affiliation: AE Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of Science, Arbuzov Str., 8, 420088 Kazan, Russia.
authors.forename: A E
authors.initials: AE
authors.lastname: Vandyukov
authors.affiliation: Laboratorie de Chimie de Coordination, CNRS, 205 route de Narbonne, 31077 Toulouse Cedex 4, France.
authors.forename: S
authors.initials: S
authors.lastname: Fuchs
authors.affiliation: Laboratorie de Chimie de Coordination, CNRS, 205 route de Narbonne, 31077 Toulouse Cedex 4, France.
authors.forename: J P
authors.initials: JP
authors.lastname: Majoral
authors.affiliation: Laboratorie de Chimie de Coordination, CNRS, 205 route de Narbonne, 31077 Toulouse Cedex 4, France.
authors.forename: A M
authors.initials: AM
authors.lastname: Caminade
authors.affiliation: AE Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of Science, Arbuzov Str., 8, 420088 Kazan, Russia. Electronic address: koval@iopc.ru.
authors.forename: V I
authors.initials: VI
authors.lastname: Kovalenko
mesh_terms: D002219:Carbamates / Q000737:chemistry*; D050091:Dendrimers / Q000737:chemistry*; D009570:Nitriles / Q000737:chemistry*; D010758:Phosphorus / Q000737:chemistry*; D017553:Phosphorus Compounds / Q000737:chemistry*; D011789:Quantum Theory; D017550:Spectroscopy, Fourier Transform Infrared; D013059:Spectrum Analysis, Raman
chemical_list: D002219:Carbamates; D050091:Dendrimers; D009570:Nitriles; D017553:Phosphorus Compounds; D010758:Phosphorus; C068226:cyclotriphosphazene ester; C070766:carbamic acid
keywords: DFT; Dendrons; Normal vibrations; Raman spectra