DFT study of Raman spectra of phosphorus-containing dendrimers built from thiophosphoryl core

V.L. Furer (1) , A.E. Vandyukov (2) , Jean Pierre Majoral (3) , A.-M. Caminade (3) , V.I. Kovalenko (2)

1 Kazan State Architect and Civil Engineering University
2 IOPC - A.E. Arbuzov Institute of Organic and Physical Chemistry
3 LCC - Laboratoire de chimie de coordination

Abstract The FT-Raman spectra of the first and second generations of phosphorus-containing dendrimers with terminal benzaldehyde and P-Cl groups have been recorded and analyzed. The structural optimization and normal mode analysis were performed for dendrimers on the basis of the density functional theory (DFT). The calculated geometrical parameters, harmonic vibrational frequencies and Raman scattering activities are predicted in a good agreement with the experimental data. The experimental Raman spectra of dendrimers were interpreted by means of potential energy distribution. Relying on DFT calculations the lines of the core, repeating units and terminal groups of dendrimers were assigned. The influence of the encirclement on the line frequencies and intensities was studied and due to the predictable, controlled and reproducible structure of dendrimers the information, usually inaccessible is obtained. The strong line at 1600 cm−1 show marked changes of intensity in dependence of aldehyde (CHO) or azomethyne (CHN) substituents in the aromatic ring. The polarizabilities and lipophilicity of the eleven generations of dendrimers were estimated based on the calculated values of the first generations.

Mots clés: Phosphorus-containing dendrimers; Raman spectra

Domaines: Chimie de coordination

V.L. Furer, A.E. Vandyukov, Jean Pierre Majoral, A.-M. Caminade, V.I. Kovalenko. DFT study of Raman spectra of phosphorus-containing dendrimers built from thiophosphoryl core. Vibrational Spectroscopy, 2013, 68, pp.61-70. ⟨10.1016/j.vibspec.2013.05.013⟩. ⟨hal-00994529⟩