Mesogenic dimer

Note 2 A liquid-erystal dimer or mesogenic dimer is sometimes known as a twin mesogen. Use of the terms dimesogenic compounds and Siamese-twin mesogen for liquid-crystal dimer or mesogenic dimer is not recommended. 

Fig. 68 Mesogenic dimer with a rigid gem-difluorocyclopropane based spacer unit (77° C) [363]...

Fig. 11 a Chemical structures of mono functional ureidotriazene 17 and ureidopyrimid-inone 18 derivatives and their mode of association into mesogenic dimers, b Bifunctional derivatives 19 and 20 and a schematic representation of their proposed self-assembly into main-chain supramolecular polymeric columns... 

S. Abraham, V.A. Mallia, K.V. Ratheesh, N. Tamaoki, S. Das, Reversible thermal and photochemical switching of liquid crystalline phases and luminescence in diphenylbutadiene-based mesogenic dimers. J. Am. Chem. Soc. 128, 7692-7698 (2006)... 

Keith, C. Reddy, R. A. Baumeister, U. Hahn, H. Lang, H. Tschierske, C. Continuous transition from antiferroelectric to ferroelectric switching liquid crystalline phases in two homologous series of bent-core mesogenic dimers based on carbosilane spacer units. J. Mater. Chem. 2006,16, 3444-3447. 

Mesogenic dimers, trimers etc. — a mesogen consisting of molecules with two, three, or more linked mesogenic units usually of identical structure. 

Fig. 7. Snapshots from a smectic-A phase of liquid crystal dimer molecules composed of two Gay-Berne mesogens linked by a flexible alkyl chain. Data from [112] supplied by Dr M R Wilson, University of Durham...

The frustration effects are implicit in many physical systems, as different as spin glass magnets, adsorbed monomolecular films and liquid crystals [32, 54, 55], In the case of polar mesogens the dipolar frustrations may be modelled by a spin system on a triangular lattice (Fig, 5), The corresponding Hamiltonian consists of a two particle dipolar potential that has competing parallel dipole and antiparallel dipole interactions [321, The system is analyzed in terms of dimers and trimers of dipoles. When the dipolar forces between two of them cancel, the third dipole experiences no overall interaction. It is free to permeate out of the layer, thus frustrating smectic order. 

Fig. 11a,b. Examples of one and two-dimensional structures for terminally fluorinated mesogens a antiparallel dimeric layering for the compounds with one terminal fluorinated tail (Diele et al. [38]) b two-dimensional (columnar) packing observed for the swallow-tailed fluorinated compounds solid lines indicate two-dimesional rectangular lattice (Lose et al. [41])... 

However, the hydrogen-bonded mesogens that are of most interest in the context of this article are those elaborated initially by Kato and Frechet in the early 1990s [24-33]. In this approach, a pyridine, which may or may not have liquid crystal properties, was hydrogen bonded with a 4-substituted benzoic acid to form a new species with its own, distinct mesomorphism. For example, complex 9 shows a SmA phase that persists to 238 °C (n = 2, m = 4), while its free component pyridine is nematic to 213 °C the component benzoic acid is also nematic (as the H-bonded dimer) to 147 °C (although note that the notional monomer would not be liquid crystalline). 

In a model study aimed at elucidating the behavior of the polymers, Watanabe found that the dimer polymethylene diol diesters of type 7 (Figure 8.18) formed smectic phases.38 When the spacer between the two mesogenic units in the dimer had an odd number of methylene groups (diester 7 has nine methylenes in the spacer), then an intercalated tilted smectic structure with all anticlinic layer interfaces was formed. This structure is often termed SmC2 in the literature. As for the B6 phase, all of the layer interfaces in this structure are equivalent, and the X-ray layer spacing is less than half the fully... 

From this discussion the clear similarity between the SmAPA and SmCsPA structures is easily seen. In addition, the suggestion of Brand et al.29 that a bilayer smectic with all anticlinic layer interfaces (the SmAPF) would produce an achiral ferroelectric smectic follows directly. The unanticipated tilt of the director in the tilt plane, leading to a chiral layer structure, seems to be a general response of the bent-core mesogens to the spontaneous nonpolar symmetry breaking occurring in these rigid dimer structures. 

Figure 8.29 Illustration showing how all-anticlinic bilayer smectic should be ferroelectric is given. In case of covalent dimers (bent-core mesogens), equilibrium tilt of director combined with anti clinic layer interfaces in bow plane provides SmCsPF ferroelectric banana structure.

Note 4 A liquid-crystal dimer with different mesogenic groups linked by a spacer is known as an asymmetric liquid-crystal dimer. 

Figure 7.39 (a) Schematic representation of discotic mesogens with only three alkoxy chains (n = 7, 8) (b) schematic representation of the star-shaped dimer. 

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