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NMR studies of carbosilane dendrimer with terminal mesogenic groups.

The 4-generation carbosilane dendrimer with terminal cyanobiphenyl mesogenic groups in dilute solution of CDCl(3) was investigated using (1)H NMR technique. The spectrum was obtained and the relaxation time, T(1), was measured in the temperature range 320-225 K. For the first time, the extrema of T(1) values were achieved for majority of the dendrimer functional groups. The values of activation energies of the dendrimer functional groups were obtained. The relaxation data for outer and inner methyl groups show that the dendrimer investigated has dense corona and hollow core. This structure is formed because the mesogenic groups do not allow terminal segments to penetrate into the dendrimer, that is, the backfolding effect is absent. The NMR spectral and relaxation data give evidence for changing conformation of the dendrimer internal segments with decreasing temperature. This reorganization is most likely connected with a change of dendrimer size. We suppose that our experimental results will provide additional information for understanding principles of dendrimer nanocontainer operation. NMR can possibly be a tool for indicating the encapsulation effect as well as the dendrimer effective size.