Fourier-transform infrared and Raman difference spectroscopy studies of the phosphorus-containing dendrimers.

FT IR and Raman spectra of 12 generations of the phosphorus-containing starburst dendrimers containing P=S and P=O bonds with terminal aldehyde and P-Cl groups were compared. The influence of the encirclement on the band frequencies and intensity is studied and due to the predictable, controlled and reproducible structure of the dendrimers the information usually inaccessible is obtained. Bands in the IR difference (G2'(P=O)-G2'(P=S)) spectra have characteristic EPR-like form. The strong band at 1600 cm(-1) show marked changes of the optical density in dependence of the aldehyde (-CH=O) or azomethyne (-CH=N-) substituents in the aromatic ring. The analysis of difference spectra enables one to assign the characteristic bands nu(P=S) and nu(P=O) for the bonds in the core, in the repeating unit and in the terminal groups of the dendrimers. This assignment is supported by the calculation of the absorption curves of the different fragments of dendrimer with the force constants and electro-optical parameters. The IR and Raman spectra of dendrimers are depended on the ratio of number terminal groups to a number of repeating units, which in its turn is strictly determined by the generation number. Thus, the marked differences in the vibrational spectra of the first successive generations aspire to zero for the higher ones. The rather rigid repeated units with little conformational flexibility define the perfect microstructure of the studied phosphorus-containing dendrimers up to the eleventh generation.