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A systematic study of the influence of generation number on the phase behavior of LC dendrimers is presented. For this purpose, phase behaviors and structures of first to fifth generations of liquid crystalline (LC) carbosilane dendrimers with 8, 16, 32, 64, and 128 terminal cyanobiphenyl groups were investigated. Investigation of thermal behavior of the LC dendrimers by means of polarizing optical microscopy, differential scanning calorimetry, and X-ray diffraction experiments reveals smectic-type mesophases over a wide temperature region. It is shown that with increasing generation number the isotropization temperature increases whereas the enthalpy of this phase transition decreases. The strongest influence of spherical molecular architecture on the phase behavior of the LC dendrimers appears at high generations. In the case of LC dendrimer of the fifth generation, it leads to the formation of two levels of a structural organization. This dendrimer forms different supramolecular nanostructures of columnar type in addition to smectic-like arrangement of mesogenic groups. Possible structures of all mesophases formed are discussed.

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