The existence of a thermotropic biaxial nematic liquid crystal phase has been a topic of great interest for almost half a century. Of the various mesogenic shapes suggested as being able to form this phase, theory has suggested that the V-shaped or "bent-core" molecule is one of the most promising candidates. In this thesis we use a simple mesogenic model of a bent-core molecule, constructed from a number of repulsive Weeks-Chandler-Andersen potentials that are assembled into a rigid V shape. Using this model we explore the spontaneous phase behaviour that occurs in a wide array of different systems of mesogens, using molecular dynamics simulations and isotropic initial conditions. We study the relationship between molecular bend angle and phase behavior for molecules constructed from 11 potentials. We find that the phase behaviour splits into two regions, above and below a critical bend angle. Molecules wider than this angle exhibit isotropic, uniaxial nematic and smectic A phases. Narrower molecules show no uniaxially aligned phases, and instead have a clustered phase with short-range ordering and no global alignment director. Increasing system size improves the smectic layering in the wider molecules, but does not affect the global alignment of the narrower molecules. Our model is extended to include the effect of the arm length of the molecule by changing the number of potentials from which the mesogens are constructed. As the molecule is reduced in size, the critical bend angle is seen to move slowly towards more linear molecules, reducing the size of the parameter space in which uniaxial nematic alignment is possible. At 5 beads, all mesophases are seen to disappear and systems remain isotropic. We also study the behaviour of binary mixtures of bent-core molecules, both of differing arm lengths and of differing bend angles. For arm length mixtures, molecules are seen to remain mixed in the isotropic and nematic phases, and phase separate on transition to a smectic phase. In addition, uniaxial nematic phases are induced in systems that have no nematic phase of their own in isolation. For mixtures of different bend angles, systems remain fully mixed in the smectic phases for differences of up to 10 degrees, and beyond this the two components begin to separate at the nematic–smectic transition.

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The recent interest in bent core liquid crystal has shown many unique physical properties, such the anomalous behaviour of the elastic constants (SplayK1, Twist K2, and BendK3). In bent core liquid crystals it is observed that K3K1). Such behaviour is analogous to calamitic liquid crystals but is in contrast to all other bent-core nematic materials reported to date. Such a result questions some of the current explanations for the elastic behaviour of bent-core materials. Using molecular field theory and atomistic modelling the different elastic behaviour predicted is again in excellent agreement with experimental results. The bend angle is again shown to be an important part in determining the physical properties of bent-core nematic liquid crystals. In a mixture from an oxadiazole dopant and calamitic host liquid crystal, it was found that a filament structure appears in the nematic phase. The filaments appear to interfere with the measurements for elastic constants. In order to understand the filament structure many methods were used including SAXS, dielectric permittivity, and DSC. It was found that the mixture had formed a gel - like phase. The gel is composed of a liquid crystal network and a liquid crystal background, not seen before in any gel system. Due to the liquid crystalline properties both the network and the background can be aligned and manipulated. The new gel phase can possess many new unique properties which warrant further studies understand further into how fundamentally the phase is forming.

In der vorliegenden Arbeit wird die Synthese und die Charakterisierung von linearen, sternförmig und dendritisch verzweigten Carbosilanen mit Me2SiH-Funktionen, vorgestellt. So konnten oligomere Carbosilane mit CH2CH2CH2SiMe2- als auch CH2CH2SiMe2-Wiederholungseinheiten dargestellt werden. Als Aufbaureaktionen dienten sowohl Alkylierungsreaktionen mit Allylmagnesiumchlorid als auch Hydrosilylierungsschritte mit Chlordimethyl- und Chlordimethylvinylsilan. Die Überführung der SiMe2Cl-Gruppen in SiMe2H-Funktionen gelang durch die Umsetzung mit Lithiumaluminiumhydrid. Besonderes Augenmerk lag auf dem Nachweis und der Abtrennung der bei diesen Reaktionen auftretenden Nebenprodukten. Einen Schwerpunkt dieser Arbeit bildete die NMR-spektroskopische Charakterisierung obiger Verbindungen, wobei insbesondere 2D-NMR-Methoden und die 29Si{1H}-NMR-Spektros-kopie zum Einsatz kamen. Für die Kohlenstoff-13-Signale dieser Verbindungen konnte aus den gewonnenen Daten der Einfluss der peripheren Substituenten in einem Inkrementensystem zusammengefasst und als Zuordnungshilfe herangezogen werden. Bisher fand ein Teil dieser Verbindungen als Bausteine in flüssigkristallinen Materialien (Arbeitskreis von Prof. Tschierske, Halle) Verwendung und erste Ergebnisse dazu werden diskutiert.

Liquid crystals are a vast and diverse class of materials which ranges from fluids made up of simple rods, polymers and solutions, to elastomers and biological organisms. Liquid crystal phases are neither crystalline, nor a ‘normal’ isotropic liquid, but lie somewhere in between these two common states of matter. Liquid crystals have found enormous use in display devices due to their electro-optic properties. In this thesis, the optical and electro-optical properties of some chiral liquid crystalline phases are studied. The optical and electro-optical behaviour of liquid crystalline blue phases has been investigated via a detailed analysis of the reflection spectrum from thin, vertical field (VF) cells. Spectral analysis in this thesis was performed using a numerical fitting technique based on the Berreman 4x4 matrix method. The validity of the technique was proved through comparisons of independent measurements with the calculated physical parameters. A novel Kerr effect measurement method was proposed in this thesis and a known material was used to verify this new method. The Kerr constant together with its dispersion relation was measured using a white light source. An unusually large Kerr constant, K, is determined in the blue phases of a non-polymer stabilized material, ~ 3x10-9 mV-2 (BPI). The large value of K is attributed to significant pre-transitional values of the dielectric anisotropy and birefringence. K follows an inverse dependence on temperature which is more marked in BPII than BPI, and we consequently suggest that the BPI demonstrates properties best suited to electro-optic devices. The field effects in blue phase include electrostriction and the influence of the Kerr effect was separated from electrostriction phenomena for the first time in this work. Finally in the Kerr effect measurements, the Kerr constant in the optically isotropic dark conglomerate phase of a bent-core material was studied for the first time, with rather low values, ~1x10-11 mV-2. The low Kerr constant can be understood in the context of the physical properties of the material. Supercooling phenomena in the blue phase were studied through an analysis of the optical properties in thin cells. Features including the Bragg reflection peak jump and hysteresis are measured through the reflection spectra. A blue phase sample with a single orientation over an area of millimeters was prepared to help the spectra study of the blue phases. Although some previous reports indicated that there may be a new blue phase in the supercooled region, we find that there is no evidence shows that the supercooled blue phase has a different structure from the BPI.Chiral molecules have been included as dopants in achiral bent-core materials to produce a range of new chiral mixtures. Different host materials and chiral dopants have been used to produce several chiral nematic materials in which the chiral nematic phase, the underlying smectic phase and the blue phases are examined. The order parameter is determined as a function of temperature in the chiral nematic phase, and compared to that determined for several calamitic materials; no discernible difference is found. A study of the pitch divergence in the chiral nematic phase of the bent-core mixtures shows interesting properties at both low temperature (as the smectic phase is approached) and at high temperatures (at the transition to the blue phase). An unusual phase separation of the chiral dopant in the mixtures is reported, and details are deduced through a comparison between different mixtures. It is found that a dopant with similar clearing point to the bent-core material has less likelihood of phase separation. Although the blue phase temperature range is extended in these mixtures in comparison with typical values for calamitic materials, it does not extend beyond 2K in any of the materials. Both blue phase I and the fog phases are observed in these chiral bent core systems, but no BPII is observed in any of the materials studied. The small k33 (~ 2.8 pN at 10 K below clearing point) in the bent-core host material is suggested as one of the reasons that the blue phase range is not enhanced as much as may have been expected from reports by other authors.

Much of the interest in bent-core compounds in the last few years has centred aroundtheir potential to form nematic liquid crystal phases, which may be both biaxial andpolar. These properties offer possibilities for nematic ferroelectric switching andnonlinear optics applications. In this work, two optical properties, the refractive indices and the second ordernonlinear optical response, were investigated in the high temperature (> 170 °C)nematic phase of a series of bent-core oxadiazole compounds, of varying chain typeand length. An experimental technique, based on the acquisition and analysis of reflectionspectra from liquid crystal cells, and capable of operating at the high temperaturesrequired, was used for the measurement of refractive indices. The extraordinaryrefractive index was found to range from 1.70 to 1.78 over the nematic phase of thebent-core compounds. The ordinary refractive index varied from 1.58 to 1.62. Bothranges of values are higher than is typically observed for rod-like liquid crystals. Thebirefringence took values from ~ 0.10, in the high temperature nematic phase, to~ 0.18, close to the underlying smectic phase. A new experiment was designed, constructed and tested for the second harmonic(SH) measurements. The dependences of the SH on temperature and on scatteringangle are well explained by the theory of SH generation by the flexoelectricpolarisation induced by thermal fluctuations of the director in the nematic phase. Themaximum conversion efficiency was measured to be very low, ~ 1/10000 of apercent. No evidence for the formation of macroscopic biaxial nematic phases was found byeither the refractive indices or SH experiments. However, for the compounds havinglong nematic phases of > 50 °C, different regimes of behaviour in the uniaxialnematic phase were revealed by the SH experiments. This atypical behaviour isconsistent with other reports on these compounds. This study cannot confirm the existence of nanoscale cybotactic clusters in thenematic phases of the bent-core compounds examined but neither is it inconsistentwith them.

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