DFT study of structure, IR and Raman spectra of the first generation dendron built from cyclotriphosphazene core with...

The FTIR and FT-Raman spectra of the first generation dendron built from the cyclotriphosphazene core, five arms -O-C(6)H(4)-CH=N-N(CH(3))-P(S) 2 bonds on the righthand side with ten carbamate terminal groups and one ester function G(v1) have been recorded. The IR and Raman spectra of the zero generation dendron G(v0) and first generation dendrimer G(1) with the same core and terminal groups were also examined. The structural optimization and normal mode analysis were performed for dendron G(v1) on the basis of the density functional theory (DFT). The calculated geometrical parameters and harmonic vibrational frequencies are predicted in a good agreement with the experimental data. It was found that G(v1) has a concave lens structure with planar -O-C(6)H(4)-CH=N-N(CH(3))-P(S) 2 bonds on the righhand side fragments and slightly non-planar cyclotriphosphazene core. The carbamate groups attached to different arms show significant deviations from a symmetrical arrangement relative to the local planes of repeating units. The experimental IR spectrum of G(v1) dendron was interpreted by means of potential energy distributions. The strong band 1604 cm(-1) shows marked changes of the optical density in dependence of the carbamate, ester or azomethyne substituents in the aromatic ring. The frequencies of ν(N-H) and ν(C=O) bands in the IR spectra reveal the presence of the different types of H-bonds in the studied dendrimers.