title: FTIR and FT-Raman spectra and DFT vibrational analysis of phosphorus-containing dendrons.
abstract: FTIR and FT-Raman spectra of four generations of phosphorus-containing dendrons with terminal aldehyde or PCl groups have been recorded and analyzed. Their spectral patterns are determined by the ratio T/R (T, the number of terminal groups; R, the number of repeated units). Bands assigned to the core, repeated units and terminal groups were separated by the difference spectroscopy method. The optimized geometry, frequencies and intensity of IR bands of G(1v) generation dendron with terminal aldehyde groups were obtained by the density functional theory (DFT). It was found that the internal skeleton of molecules exists in a single stable conformation with planar O-C(6)H(4)-CHN-N(CH(3))-P(S) fragments, but terminal groups may adopt the t,g,g- and t,-g,g-rotational isomers. The t,-g,g-conformer is 0.74 kcal/mol less stable compared to the t,g,g-conformer. The bond length and bond angles obtained by DFT show the best agreement with experimental data. Relying on DFT calculations a complete assignment of vibrations is proposed for different parts of the studied dendrons. The calculated frequencies and intensity of IR bands of the t,g,g- and t,-g,g-conformers of G(1v) are found to be in reasonable agreement with the experimental results. The most reactive site in dendron is the core function and vinyl group is preferred for nucleophilic attack. In dendrimer the most reactive are the terminal groups.
authors.affiliation: Kazan State Architect and Civil Engineering University, Zelenaya 1, Kazan 420043, Russia. furer@ksaba.ru
authors.forename: V L
authors.initials: VL
authors.lastname: Furer
authors.forename: I I
authors.initials: II
authors.lastname: Vandyukova
authors.forename: A E
authors.initials: AE
authors.lastname: Vandyukov
authors.forename: J P
authors.initials: JP
authors.lastname: Majoral
authors.forename: A M
authors.initials: AM
authors.lastname: Caminade
authors.forename: V I
authors.initials: VI
authors.lastname: Kovalenko
mesh_terms: D018360:Crystallography, X-Ray; D050091:Dendrimers / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D010758:Phosphorus / Q000737:chemistry; D017550:Spectroscopy, Fourier Transform Infrared; D013059:Spectrum Analysis, Raman; D013816:Thermodynamics
chemical_list: D050091:Dendrimers; D010758:Phosphorus