ABSTRACT
Broadband dielectric spectroscopy (10(3) Hz-1.8 × 10(9) Hz) has been performed on the odd nonsymmetric liquid crystal dimers of the series α-(4-cyanobiphenyl-4'-oxy)-ω-(1-pyreniminebenzylidene-4'-oxy) alkanes (CBOnO.Py) with n ranging from 3 to 11, as a function of temperature. A previous thermal behavior study through heat capacity measurements has been made. Dielectric measurements enable us to obtain information about the molecular dynamics in the nematic mesophase as well as in the isotropic phase. Two orientations (parallel and perpendicular) of the molecular director with regard to the probe electric field have been investigated. In the nematic mesophase, the dielectric anisotropy is revealed to be positive for all studied compounds. Measurements of the parallel component of the dielectric permittivity are well-explained by means of the molecular theory of dielectric relaxation in nematic dimers (Stocchero, M.; Ferrarini, A.; Moro, G. J.; Dunmur, D. A.; Luckhurst, G. R. J. Chem. Phys., 2004, 121(16), 8079). The dimer is seen as a mixture of cis and trans conformers, and the model allows us to estimate their relative populations at each temperature. The main molecular motions are interpreted by the model as independent end-overend rotations of each terminal semirigid unit of the dimer.
ABSTRACT
Broadband dielectric spectroscopy (10(3) to 1.8 × 10(9) Hz) and specific heat measurements have been performed on the odd nonsymmetric liquid crystal dimer α-(4-cyanobiphenyl-4'-oxy)-ω-(1-pyreniminebenzylidene-4'-oxy)undecane (CBO11O·Py), as a function of temperature. The mesogenic behavior is restricted to a nematic mesophase which can be supercooled down to its corresponding glassy state if the cooling rate is fast enough (no less than 15 K·min(-1)). Dielectric measurements enable us to obtain the static permittivity and information about the molecular dynamics in the nematic mesophase as well as in the isotropic phase and across the isotropic-to-nematic phase transition. Two orientations (parallel and perpendicular) of the molecular director with regard to the probe electric field have been investigated. In the nematic mesophase, the dielectric anisotropy is revealed to be positive. Measurements of the parallel component of the dielectric permittivity are well explained by means of the molecular theory of dielectric relaxation in nematic dimers (J. Chem. Phys. 2004, 121 (16), 8079). The dimer is seen as a mixture of cis and trans conformers, and the model allows us to estimate their relative populations at each temperature. The main molecular motions are interpreted by the model as independent end-overend rotations of each terminal semirigid unit of the dimer. The nematic-to-isotropic phase transition has been exhaustively studied from the accurate evolution of the specific-heat and the static dielectric permittivity data. It has been concluded that the transition is first order in nature and follows the tricritical hypothesis. As a consequence, the nematic mesophase has been characterized as uniaxial despite the biaxiality and flexibility of the dimer molecule.
ABSTRACT
Three bent-core liquid-crystal compounds presenting the unusual columnar B1 to tilted polar smectic (Sm-CP or B2) phase transition are studied through small-angle x-ray diffraction on aligned samples. The well-established character of the smectic phase helps to characterize the structural changes during the transition. A mechanism for this transition is proposed, which accounts for the low enthalpy usually observed in this process. The B1 phase is found to possess a great degree of lamellarization, with pseudosmectic ferroelectric layers along the crystallographic (11) planes. As a consequence of these observations a distribution of the block polarizations in the columnar structure is proposed.
ABSTRACT
We report on a series of three bent-core liquid crystals containing tetrathiafulvalene units. Their characterization consisted of electro-optical observations, second-harmonic generation (SHG) analysis, and x-ray diffraction measurements. Compound I exhibits a lamellar optically isotropic phase on cooling from the isotropic liquid and undergoes a nonreversible field-induced transition to a birefringent state. The two others present two-dimensional structural periodicities, being only compound II switchable. Additionally, the electron density maps of compounds II and III have been obtained based on the analysis of the x-ray diffraction intensities. According to SHG measurements the ground state is antiferroelectric in the three compounds. A quite good SHG performance is found in compounds I and II.
ABSTRACT
A bent-core mesogen containing a tetrathiafulvalene group is studied. The mesophase is an optically isotropic spongelike smectic phase without optical activity. The material responds to uv light in a peculiar way, showing photoconductivity and, in some circumstances, changing its mesomorphic properties. Under an electric field, large chiral domains are segregated from an initial racemic phase within a few minutes.
ABSTRACT
An experimental study of the B1-B2 transition is carried out in a bent-core liquid crystal. The study is essentially based on x-ray measurements as a function of temperature. The B1-B2 transition is extremely unusual and implies a deep structural change from a columnar phase to a lamellar phase. We have found that the B1 phase in our compound is similar to the so-called B1 reversed phase, with an additional splay of the polarization in the columns. On approaching the B2 phase the width of the cross section of the columns increases. The transition is clearly first order, with a large hysteresis though the enthalpy content is very small. A possible mechanism for the transition is briefly sketched.
ABSTRACT
A structural investigation of the compound 8-OPIMB-NO2 is carried out. This material is a mesogen formed by bent-core molecules where the so-called B7 phase was originally proposed. X-ray data are successfully indexed in terms of a oblique two-dimensional lattice. Using additional information from optical second harmonic generation several possible structural models are proposed. The models are based on molecular packing considerations. All these structures are clearly different from those of other materials previously classified as B7. The necessity of a revised nomenclature for classifying the structures of these compounds is pointed out.
ABSTRACT
We report experimental results on two bent-shaped mesogens showing the B1 phase. Contrary to the conventional B1 structures, we have found that our compounds display a clear electro-optic effect in this phase. Under the influence of a 100-Hz square-wave electric field of moderate amplitude, an increase of the birefringence is observed. However, no switching current is detected, indicating that the materials remain antiferroelectric. For high enough fields, a drastic change in the texture occurs. This change is a phase transition to a B2 phase, and shows the typical antiferroelectric switching of this phase. The induced B2 phase has been identified to be homochiral. Upon removal of the field, the B1 structure is recovered. Our study is based on differential scanning calorimetry, x-ray, electro-optics, polarization reversal, and dielectric measurements.
ABSTRACT
A liquid crystal material of bent-core molecules is investigated by means of optical texture observations, x-ray measurements, and miscibility studies. While the x-ray and miscibility data point towards a B2 phase, the texture is however unusual, showing optical isotropy and segregation in two domains with opposite gyrations. It is shown that the texture can be interpreted successfully in terms of a smectic-C(A)P(A) structure in small domains with random orientations. The optical activity data are also explained semiquantitatively.
Subject(s)
Polymers/chemistry , Biophysical Phenomena , Biophysics , Light , Models, Chemical , Models, Theoretical , X-RaysABSTRACT
We report the observation of a transition from the antiferroelectric B2 phase to a ferroelectric phase in a liquid crystal composed of achiral bent-core (banana-shaped) molecules. The transition is induced by an electric field of magnitude larger than the switching threshold and is not reversible, i.e., the original B2 phase does not reappear upon field removal. The transformation is accompanied by a dramatic texture change, resulting in an almost optically isotropic structure in the absence of field. The ferroelectric character assigned to the structure is based on the electro-optic behavior of the material and on previously reported dielectric measurements. A short-pitch smectic-C*-type structure is proposed for the ferroelectric phase.
ABSTRACT
Second-harmonic generation (SHG) measurements have been performed in the B2 phase of the achiral banana-shaped molecule with n=12 alkoxy end chains (P-12-O-PIMB). A quantitative value of the nonlinear efficiency has been obtained from SHG curves at oblique incidences, taking into account that the signal is generated by a random orientation of different domains. In the B4 phase, circular dichroism, optical absorption and SHG studies have been carried out. It has been found that there are no simple helical arrangements giving rise to selective reflection in the visible region of the spectrum. In addition, some unusual features of the SHG behavior are pointed out. It is concluded that the phase is intrinsically inactive for the SHG process. The detected signal is due to the presence of some birefringent inclusions that are created at the B2 to B4 transition and slowly disappear while the sample is maintained within the B4 phase. A structural model for these inclusions is presented.