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(CO) 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(CO) 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.