Induced discotic phases

The most obvious family of compounds able to induce columnar phases is that constituted by the macrocyclic compounds which often possess a discoid molecular shape. The ability of macrocyclic systems to stack and to self-assemble into columnar mesophases confers on these systems the properties required for potential utilization in molecular devices based on photonics, electronics, or low-dimensional ionic transport. The search for new discotic mesogens is thus still of current interest, in order to improve their chemical, thermal, and photophysical stabihty, and new families of discogenic materials appear regularly. 

Complexes of polymeric acceptors and monomeric donors are also effective in inducing discotic PLCs. This was shown, in particular, for a main chain polyester into which TNF was incorporated, mixed with a triphenylene derivative [73]. In order to avoid phase separation, the donor concentration must exceed the acceptor concentration by a mole ratio of at least 3 1. It was also demonstrated that the alkyl spacer length in the main chain can be critical to the definition and stability of the discotic mesophase obtained. As illustrated in Figure 3.32, spacer lengths which are either too short or too long can inhibit the incorporation of the polymeric acceptor into the donor columns, the... 

As mentioned in Section 3.1, phase biaxiality may be described by a set of microscopic order parameters when the mesogen is a rigid uniaxial particle, where a and (5 refer to the space-fixed axes x y z). Biaxial nematics [3.31], some smectic phases, like smectic C, and certain discotic phases [3.32] exhibit phase biaxiality. The order parameters 5, , and 5, , are different in these phases. NMR may be used to detect phase biaxiality through measurement of a non-zero motionally induced asymmetry parameter in nuclear spin interactions such as dipole-dipole and electric quadrupole interactions. To see how exists in biaxial mesophases, the previous discussion on motional averaging of spin Hamiltonian is gen-... 

The formation of charge transfer (EDA) complexes between suitable components may induce columnar [327-329] or nematic discotic phases [329-331]. Also the formation of intramolecular EDA complexes in twin molecules can influence the mesomorphic properties substantially [310,332]. 

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]. 

Just as chiral induction can be realised in discotic liquid crystals, it can also be realised in assemblies of disc-like molecules or disc-like aggregates. As far as molecules are concerned, C3-symmetrical trisamides (Fig. 15), which actually exhibit discotic liquid crystalline phases, also form chiral columnar stacks through it-it interactions when dissolved in apolar solvents, which are depicted schematically in Fig. 15 [121]. An achiral compound of this type (15) exhibits no optical activity in dodecane, but when the compound is dissolved in the chiral CR)-(-)-2,6-dimelhyloctanc significant Cotton effects (only slightly less intense than those observed in a chiral derivative) are detected. The chiral disc-like trisamide 16 can also be used as a dopant at concentrations as low as 2.5% to induce supramolecular chirality in the stacks of achiral compound. In this case, the presence of the additional hydrogen... 

Recent work focuses on non-classical mesogenes which are built up by self-assembly. One example is a family of polymers containing disk-like groups which form no liquid crystalline phase, but ean act as an electron acceptor or donor. Charge transfer complexation with a complementary low molecular mass compound induces nematic or columnar discotic liquid crystalline order [153,154]. Figure 13 demonstrates this with the example of a polyester, bearing electron-rich tetra(alkoxy)tri-phenylene-units in the main chain, mixed with the electron deficient aromatic 2,4,7-trinitro-9-fluorenone (TNF). While the pure polymer shows a non-ordered isotropic melt, a columnar phase appears on addition of TNF. 

In discotics, the interdisk stacking interaction is several orders of magnitude stronger than the inter-columnar interactions, because of the phase separation induced by the side-chains whose van der Waals interactions are much weaker. Generally, long polymers are obtained via discotics that have strong and specific intermolecular interactions, either via a large aromatic core or via additional specific intermolecular... 

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). ... 

Four chiral homologous complexes were also prepared. None of the palladium complexes showed mesomorphic properties, whereas a monotropic chiral discotic nematic phase was observed for the platinum complex (Table 18). The absence of mesomorphism for the dinuclear palladium complexes may be due to the type of chiral chain used, which differed from that used for the platinum system. All of the complexes form charge-transfer complexes with TNF. A Colh phase was induced for the two halo-bridged palladium complexes and for the platinum complex, as was observed for their non-chiral analogs. Flowever, the chiral nematic phase of the platinum compound was suppressed. At low TNF content, a chiral Nq phase was stabilized for the thiocyanato-bridged compound along with a non-chiral No phase at higher concentration. 

Results were also described from studies which introduced lateral substituents into these complexes and in one paper the effect of introducing lateral alkanoate groups was reported (113). " The use of lateral alkanoates had been described previously by Maitlis and co-workers in palladium complexes of 4-alkoxystilbazoles (Section 7.9.14.3.6(iv)) and had been shown to induce the formation of liquid crystal nematic phases. In the present situation where the complex was polycatenar, it was not clear whether the chains would act to increase the volume of the core of the polycatenar mesogen or simply as extra chains, so rendering the complex more classically discotic. In fact, the answer was neither and at all chain lengths (n and m) and degrees of substitution (R = H or OC H2 +i) where mesomorphism was observed, a nematic phase was seen at or near room temperature. This behavior was somewhat puzzling and is so far without explanation. 

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