RESUMO
When a chiral dopant is dissolved in an achiral liquid crystal medium, the whole sample organizes into a helical structure with a characteristic length-scale of the order of microns. The relation between chirality at these quite different length-scales can be rationalized by a relatively simple model, which retains the relevant factors coming into play: the molecular shape of the chiral dopant, which controls the chirality of short range intermolecular interactions, and the elastic properties of the nematic environment, which control the restoring torques opposing distortion of the director. In this tutorial review the relation between molecular and phase chirality will be reviewed and several applications of the chiral doping of nematic LCs will be discussed. These range from the exploitation of the amplified molecular chirality for stereochemical purposes (e.g., the determination of the absolute configuration or the enantiomeric excess), to newer applications in physico-chemical fields. The latter take advantage of the periodicity of the chiral field, with length-scales ranging from hundreds to thousands of nanometres, which characterise the cholesteric phase.
RESUMO
Temperature-dependent studies on the diastereoselective nucleophilic addition of n- BuLi to alpha-chiral aldehydes as (S)-O-(t-butyl-dimethylsilyl)lactal, (S)-O-(t-butyl-dimethylsilyl) mandelic aldehyde, and (R)-2-phenylpropanal in n-decane and n-dodecane reveal dynamic solvation phenomena with the presence of inversion temperatures (T(inv)) in the Eyring plots of ln (anti/syn) vs. 1/ T. These dynamic solvent effects were disclosed by temperature-dependent studies of the (13)C NMR, CD, and UV spectra of the starting aldehydes in solution of n-decane and n-dodecane. The concomitant presence of three peculiar temperatures T(CD), T(UV), and T(NMR), whose values are identical and match T(inv), clearly confirms our earlier interpretation of the solvent-dependent nature of T(inv). The inversion temperature, as well as T(CD), T(UV), and T(NMR) represents the interconversion temperature of two different solvation clusters which act as two different supramolecules with different stereoselectivities.