ABSTRACT
We used proton ( (1)H nuclear magnetic relaxation (NMR) dispersions to study the molecular dynamics in the isotropic phase and mesophases (nematic and columnar hexagonal) of a supermesogenic octapode formed by laterally connecting calamitic mesogens to an inorganic silsesquioxane cube through flexible spacers. The dispersions of the spin-lattice relaxation time (T(1)) are interpreted through relaxation mechanisms used for the study of molecular dynamics in low-molar-mass liquid crystals but adapted to the case of liquid crystalline supermolecules. At high frequencies (above 10MHz) the behaviour of the T(1) with the Larmor frequency is similar for all phases and is ascribed to local reorientations and/or rotations. At intermediate and low frequencies (below 10MHz) our results show notable differences in the T(1) behaviour with respect to the mesophases. The nematic (N) and isotropic (Iso) phases' low-frequency results are similar and are interpreted for both phases in terms of order director fluctuations (ODF), revealing that even in the isotropic phase local nematic order is detected by proton NMR relaxometry. Local nematic order in the Iso phase is interpreted in terms of the presence of nematic cybotactic clusters induced by the interdigitation of mesogens that is promoted by the silsesquioxane octapode molecular structure. In the columnar hexagonal (Col (h) phase, the T(1) dispersions show that elastic columnar deformations (ECD) dominate the nuclear magnetic relaxation below 10MHz. This result shows that the columnar packing of the octapode clearly restricts the collective fluctuations of the mesogenic units inspite of their local nematic order.
ABSTRACT
We present the first results obtained by proton ((1)H) nuclear magnetic relaxation studies of molecular dynamics in a supermolecular liquid-crystal dendrimer exhibiting columnar rectangular and smectic-A phases. The (1)H spin-lattice relaxation time (T(1)) dispersions are interpreted using two relaxation mechanisms associated with collective motions and local molecular reorientations of the dendritic segments in the low- and high-frequency ranges, respectively. The T(1) values show a drop around 2.3 MHz that is attributed to a contribution coming from cross-relaxation between (1)H and nitrogen nuclear spins. In the high-frequency range the motions appear to be of similar nature in both mesophases and are ascribed to reorientations of dendritic segments (belonging to the core and/or to the mesogenic units) characterized by two correlation times. Notable differences in the dynamics between the columnar and layered phases are observed in the low-frequency range. Depending on the mesophase they are discussed in terms of elastic deformations of the columns and layer undulations. In this study we find that the dendritic core influences the dynamics of the mesogenic units both for local and collective motions. These results can be understood in terms of spatial constraints imposed by the dendritic architecture and by the supermolecular arrangement in the mesophases.
