Chiral columnar mesophases

The prime requirement for the formation of a thermotropic liquid crystal is an anisotropy in the molecular shape. It is to be expected, therefore, that disc-like molecules as well as rod-like molecules should exhibit liquid crystal behaviour. Indeed this possibility was appreciated many years ago by Vorlander [56] although it was not until relatively recently that the first examples of discotic liquid crystals were reported by Chandrasekhar et al. [57]. It is now recognised that discotic molecules can form a variety of columnar mesophases as well as nematic and chiral nematic phases [58]. 

Trzaska and co-workers showed a similar propeller mechanism for the formation of helical columns from disclike metallomesogens (29-31).34 These metallomesogens also have C3 symmetry and 30 and 31 are provided with chiral side chains. In the hexagonal columnar mesophase these chiral side chains induce a Cotton effect in the chromophore of the helically arranged core. Heating the mesophase to the isotropic liquid results in the disappearance of the Cotton effect because of the loss of helical order. This effect illustrates the need for the molecules to be positionally ordered in order for the side-chain chirality to be transferred to the supramolecular column. 

A helical arrangement within columns was also found for other metal 3-diketonate complexes provided with chiral side chains (32) by Serrano and co-workers.35,36 These compounds form rectangular columnar mesophases with helical order within the columns. A spin-coated sample of 32 showed a positive exciton-splitted signal in the CD spectra, which was interpreted as a left-handed (M) helix. Annealing of the film resulted in much higher optical activities and a shift of the absorption maxima. The observed optical changes clearly point to a chiral organization of the columns in the mesophase. 

Nuckolls and Katz have synthesized discotic liquid crystalline molecules in which the core is a helix in its own right.37 Nonracemic helicene 33 was found to assemble into a columnar mesophase in which the helicenes stack on top of each other. CD spectroscopy showed a strong increase of the Cotton effect upon going from the molecularly dissolved state to the aggregated state, exhibiting an amplification of chirality. These helical columns give rise to a strong expression of chirality because the intrinsic shape of the helicenes... 

Note 4 There also exist chiral columnar rectangular mesophases, with the molecular discs tilted periodically in the columns and with the tilt directions changing regularly down the columns. 

Note 5 If the mesogenic side-groups are rod-like (calamitic) in nature, the resulting polymer may, depending upon its detailed structure, exhibit any of the common types of calamitic mesophases nematic, chiral nematic or smectic. Side-on fixed SGPLC, however, are predominantly nematic or chiral nematic in character. Similarly, disc-shaped side-groups tend to promote discotic nematic or columnar mesophases while amphiphilic side-chains tend to promote amphiphilic or lyotropic mesophases. 

Compound 114d possesses significantly lower transition temperatures (Scheme 60) due to the branched side chains [126]. A columnar phase is present even below room temperature. At 14 °C, anew chiral columnar phase was observed while above 111 °C, an achiral columnar rectangular phase was observed. The spiral-pattern texture of 114d in the chiral Col mesophase is shown in Fig. 17. 

Metallomesogens have been shown to form helical supramolecular organisations in their mesophases [95]. Chiral oxazoline complexes with various metal ions and six alkyl chains did not show LC behaviour, but when mixed with trinitrofluorenone form achiral smectic A phases [96]. Furthermore, when a branch was included in the structure of the ligands (Fig. 12) the corresponding complexes with copper(II) and palladium(II) form columnar mesophases which have a helical organisation [97]. The presence of the stereogenic centre near the central metal ion in these complexes (Fig. 12) is enough to cause the parallel molecules to stack in a tilted manner with... 

Spontaneous polarisation can also be observed for chiral discotic metallomesogens forming columnar mesophases, when the chiral molecules are tilted with respect to the column axis. The tilt induces a dipole moment within the plane of the molecule. A net macroscopic polarisation can be obtained for rectangular columnar phases with Cz or P2i symmetry. Serrano and Sierra reported on ferroelectric switching in the columnar mesophase for chiral /3-diketonate complexes (Figure 2.52). ... 

Similarly to the molecular engineering of calamitic molecules to produce ferroelectric smectic C phases [129], disk-like molecules with chiral peripheral chains tilted with respect to the columnar axis were predicted to lead to ferroelectric columnar mesophases [130]. Indeed, as it is the case with all flat disk-shaped mesogenic molecules, the tilt is mainly associated with the flat rigid aromatic cores of the molecules, the side-chains being in a disordered state around the columnar core. Thus, the nearest part of the chains from the cores makes an angle with the plane of the tilted aromatic part of the molecules. If the chiral centre and the dipole moment are located close to the core, then each column possesses a non-zero time averaged dipole moment, and therefore a spontaneous polarization. For reasons of symmetry, this polarization must be, on average, perpendicular to both the columnar axis and to the tilt direction in other words, the polarization is parallel to the axis about which the disk-shaped molecules rotate when they tilt as shown in Fig. 29. 

In addition, these complexes, except 49a and 50a, form lyotropic columnar (oblique) and nematic phases when dissolved in linear, apolar organic solvents (alkanes) over wide temperature and concentration ranges. Interestingly, for some of them, 49b-c, an unexpected transition between two lyotropic nematic phases has been observed, for which a model has recently be proposed [93]. As for 48, formation of lyotropic nematic and columnar mesophases is also extended by n-n interactions with electron-acceptors, such as TNF, in apolar solvents (pentadecane). Induction of chiral nematic phases by charge transfer interactions, in a ternary mixture (49b/alkane/TAPA TAPA is 2-(2,4,5,7-tetranitro-9-fluorenylideneaminooxy)-propionic acid and is used (and is available commercially) enantiomerically pure), has recently been demonstrated for the first time [94], and opens new perspective for producing chiral nematic phase of disc-like compounds. 

I.M. Saez, J.W. Goodby, R.M. Richardson, A liquid crystalline silsesquioxane dendrimer exhibiting chiral nematic and columnar mesophases. Chem. Eur. J. 7, 2758-2764 (2001)... 

More recently, chiral discotic materials that exhibit tilted columnar mesophases have attracted attention because of their potential for ferroelectric switching. A spontaneous polarisation is generated because of the restriction in rotation of the peripheral chiral chains. 

Optically active esters of benzene, triphenylene and truxene have been studied [40], The triphenylene and truxene derivatives (structures 2 and 4, respectively, with R = (-h)- or (-)-CH3-(CH2)5-CH(CH3)-CH2-CO O) do show mesophases, but of the non-chiral columnar type. In other words, this chiral substituent does not change the nature of the phases. The benzene derivative is non-mesomorphic. However, when these compounds are mixed with... 

In addition, structures with an iron complex in place of the central ring in series such as 17,18, and 19 may also exhibit nematic, SmC, and columnar mesophases. These new metallomesogens are of interest because they are easily prepared in optically pure forms and therefore can lead to ferroelectric properties in the chiral SmC form. For example, complex 21 with n = 11 exhibits SmC and cholesteric properties (Cr 52.5°C SmC 111°C N 119 I), while only a hexagonal columnar phase is observed with n = 12 (Cr60.5°C 112.5 I)... 

By using the chiral electron acceptor (-)-TAPA, even the cholesteric versions of the nematic discotic phase Ng or of the nematic columnar one Ncoi can be obtained, for example, by doping a nematic discotic pentayne ether with up to 30 mol% (-)-TA-PA or by inducing the N oi phase in a ternary mixture composed of pentayne ether (4) (n = 16) with TNF and (-)-TAPA the latter electron acceptor does not itself lead to the induction of a columnar mesophase with such pentayne donors [26, 59 d]. 

Induction of chirality in No phases was also shown to be possible using charge transfer interactions, via jt-jt stacking. The binary mixture of mesogen 8, which is electron rich, with chiral electron-deficient molecule 9 was shown to induce a twist in the mesophase.15 Furthermore, nonmesogenic 8 gave rise to a cholesteric mesophase, denoted as being of the columnar type (N ), when present in a ternary system with TNF (trinitrofluorenone, an electron acceptor)... 

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