Mesophase structure and behaviour in bulk and restricted geometry of a dimeric compound exhibiting a nematic-nematic transition.

We present structural studies of a dimeric compound composed of a central heptyl spacer linking two mesogens consisting of terphenyl units at which two adjacent fluoro groups are attached to each central ring. The terminal rings are linked to pentyl chains as terminal groups. The material exhibits a nematic-nematic transition and a low temperature modulated phase. The higher temperature nematic phase was found to exhibit an anomaly of the bend elastic constant similar to that of the dimers with N-Ntb phase sequence, and the physical properties of the low-temperature nematic phase are similar to those of the known Ntb materials. The structure of the low-temperature modulated smectic/columnar phase is described together with its ability to form freely suspended films and fibres. The relation of the modulated structure to the fibre formation and to the appearance of the labyrinthine instability in freely-suspended films is discussed.

Mesomorphism and electrochemistry of thienoviologen liquid crystals.

The thienoviologen series 4,4'-(2,2'-bithiophene-5,5'-diyl)bis(1-alkylpridinium)X2, with = counterion is a new class of electron acceptor materials which show very interesting electrochromic and electrofluorescence properties. Depending on the length, m, of the promesogenic alkyl chains, and on the counterion, thienoviologens might become liquid crystals. Here, we present the mesomorphic behaviour, and the electrochemical and spectroelectrochemical properties in solution of new thienoviologens of the series and (I = iodide; NTf2(-) = bis(tri-fuoromethylsulfonyl)imide) with m = 8, 12. Interestingly, we found that only the compounds are liquid crystals, exhibiting a calamitic behaviour in contrast to the homologous compounds of the series with m = 9-11 and X = NTf2(-), which showed columnar rectangular mesophases. The electrochemical study here reported allowed us to explain for the first time the anomalous behaviour of these thienoviologens already observed in cyclic voltammetry, where two apparently irreversible redox processes occur. This can be explained by a comproportionation reaction in which the neutral species rapidly reduces the dication to the radical-cation, due to its strong reducing power. Electrochemical reduction of the thienoviologens causes electrochromism since a new absorption band, occurring at 660 nm in the electronic spectra, appears with the negative potential bias applied. With a LUMO level of 3.64 eV, similar to those of the C60 and of other n-type materials, these compounds can find applications in several electronics devices, where their liquid crystalline properties can be used to control film morphology and geometry, provided they have good electron mobility.

Structure studies of the nematic phase formed by bent-core molecules.

In recent years there are several reports showing that bent-core mesogenic molecules are able to form biaxial nematic phase in which molecular rotation around the long molecular axis is strongly hindered. The x-ray pattern with azimuthally split signals at low angle region of diffraction is usually given as evidence for the biaxial nematic phase. We show experimentally and theoretically that such x-ray pattern is due to the local smectic- C fluctuations ("cybotactic" groups) in the uniaxial nematic phase.