One of the defining characteristics of the twist-bend nematic phase, formed by the methylene-linked liquid crystal dimer 1″,7″-bis(4-cyanobiphenyl-4'-yl) heptane (CB7CB), is its chirality. This new nematic phase, predicted by Dozov, is of particular interest because although the constituent molecules are achiral the phase itself is chiral. Here, we describe the use of NMR spectroscopy to determine experimentally whether in reality the phase is chiral or not. The basis of this novel procedure is that the equivalence of the protons or deuterons in a prochiral methylene group in a nematic phase with D∞h symmetry is lost in a chiral phase because its symmetry is reduced to D∞ on removal of the mirror plane. Recording proton-enhanced local field (PELF) NMR experiments shows that in the standard nematic phase all of the methylene groups in the heptane spacer have equivalent pairs of C-H groups but this equivalence is lost for the six prochiral methylene groups with their enantiotopic protons on passing to the twist-bend nematic. Strikingly, this equivalence is not lost for the central methylene group where the two protons are homotopic. We also show how the phase chirality can be demonstrated with probe molecules which contain deuteriated prochiral methylene groups, using 4-octyl-4'-cyanobiphenyl-d2, perdeuteroacenaphthene-d10, and acenaphthene-d4 as examples. For the standard nematic phase deuterium, NMR shows that the deuterons in these methylene groups are equivalent but, as expected, in the twist-bend nematic phase this equivalence is lost. The deuterium NMR spectra of these probe molecules dissolved in CB7CB have been recorded from the isotropic phase, through the nematic and deep into the supercooled twist-bend nematic.
The proton and natural abundance carbon-13 NMR spectra of
(±)-3-butyn-2-ol enriched in the S enantiomer
(ee = 72%) and oriented in the chiral nematic liquid
crystalline phase of
[poly(γ-benzyl-l-glutamate)/deuterochloroform] have been obtained and analyzed. The residual
1H−H and 1H−13C
dipolar couplings
were corrected for the effects of molecular harmonic vibrational
motions and used to determine the r
α
structure
and the five independent order parameters,
S
αβ, for each enantiomer. It is shown
that the data is consistent
with the two enantiomers having an identical
r
α structure, but the order matrices differ in
both the magnitudes
of their elements and the orientation of their principal
axes.
The sets of residual dipolar couplings between carbon and hydrogen nuclei obtained from the proton-encoded (13)C 2D NMR experiment are used to investigate the conformational changes which occur when the achiral symmetric liquid crystal dimer CB7CB changes from the achiral nematic to the chiral twist-bend nematic phase. It is found that these changes are a consequence of the chirality of the twist-bend nematic phase, rather than being the driving force for the stability of this phase.
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