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Phase transitions and molecular mobility of a discotic liquid crystal under nanoscale confinement
(2013)
The phase behavior and the molecular dynamics of a pyrene-based discotic liquid crystal when confined in nanoporous aluminum membranes with different pore sizes is studied by broadband dielectric spectroscopy and differential scanning calorimetry. In confinement the two phase transitions between plastic crystalline and hexagonal ordered phase at lower and from the latter to an isotropic state at higher temperatures are also observed, but two different phase structures close to the wall and in the pore center are evidenced by two peaks in the heat flow for the first time. While the former peak is independent of the pore size, the depression of the phase transition temperatures of the latter ones can be described by the GibbsThomson equation. With decreasing pore size for both phase transitions the transition enthalpies decrease. A critical pore size for phase transformation of about 20 nm is estimated from the pore size dependence of the transition enthalpies. Like for the bulk, an a-relaxation is also observed in confinement. At the phase transition its relaxation rates show a discontinuity from which a dielectric phase transition temperature can be extracted. For temperatures above and below the phase transition the temperature of the relaxation rate can be approximated by an Arrhenius equation. The pore size dependence of the estimated apparent activation energies is ascribed to the interplay between pore size and interaction effects. The cooperative nature of the underlying molecular dynamics is indicated by the occurrence of the well-known compensation law.
The molecular dynamics of the discotic liquid crystal pyrene-1,3,6,8-tetracarboxylic tetra(2-ethylhexyl)ester is studied by dielectric relaxation and specific heat spectroscopy. Dielectric spectroscopy shows 3 processes: a β-relaxation at low temperatures and an α-relaxation in the temperature range of the mesophases followed by conductivity. The dielectric α-relaxation is assigned to a restricted glassy dynamics in the plastic crystal as well as in the liquid crystalline phase. The obtained different Vogel–Fulcher–Tammann laws (different Vogel temperatures and fragility) are related to the different restrictions of the dipolar fluctuations in the corresponding phases. By means of specific heat spectroscopy glassy dynamics is also detected in the plastic crystalline phase but with quite a different temperature dependence of the relaxation times. This is discussed considering the different probes involved and how they are influenced by the structure. In the frame of the fluctuation approach a correlation length of glassy dynamics is calculated to 0.78 nm which corresponds to the core–core distance estimated by X-ray scattering.
Hexakis(n-alkyloxy)triphenylene) (HATn) consisting of an aromatic triphenylene core and alkyl side chains are model discotic liquid crystal (DLC) systems forming a columnar mesophase. In the mesophase, the molecules of HATn self-assemble in columns, which has one-dimensional high charge carrier mobility along the columns. Here, a homologous series of HATn with different length of the alkyl chain (n = 5,6,8,10,12) is investigated using differential scanning calorimetry (DSC), broadband dielectric spectroscopy (BDS) and advanced calorimetric techniques including fast scanning calorimetry (FSC) and specific heat spectroscopy (SHS). The investigation of the phase behavior was done utilizing DSC experiments and the influence of the alkyl chain length on the phase behavior was revealed. By the dielectric investigations probing the molecular mobility, a c-relaxation due to localized fluctuations as well as two glassy dynamics, the acore- and aalkyl-relaxation, were observed in the temperature range of the plastic crystalline phase. Moreover, the observed glassy dynamics were further studied employing advanced calorimetry. All observed relaxation processes are attributed to the possible specific molecular fluctuations and discussed in detail. From the results a transition at around n = 8 from a rigid constrained (n = 5,6) to a softer system (n = 10,12) was revealed with increasing alkyl chain length. A counterbalance of two competing effects of a polyethylene-like behavior of the alkyl chains in the intercolumnar domains and self-organized confinement is discussed in the context of a hindered glass transition.
Hexakis(n-alkyloxy)triphenylene) (HATn) consisting of an aromatic triphenylene core and alkyl side chains are model discotic liquid crystal (DLC) systems forming a columnar mesophase. In the mesophase, the molecules of HATn self-assemble in columns, which has one-dimensional high charge carrier mobility along the columns. Here, a homologous series of HATn with different length of the alkyl chain (n=5,6,8,10,12) is investigated using differential scanning calorimetry (DSC), broadband dielectric spectroscopy (BDS) and advanced calorimetric techniques including fast scanning calorimetry (FSC) and specific heat spectroscopy (SHS). The investigation of the phase behavior was done utilizing DSC experiments and the influence of the alkyl chain length on the phase behavior was revealed. By the dielectric investigations a γ-relaxation due to localized fluctuations as well as two glassy dynamics the αcore and αalkyl relaxation were observed in the temperature range of the plastic crystalline phase. Moreover, the observed glassy dynamics were further studied employing advanced calorimetry. All observed relaxation processes are attributed to the possible specific molecular fluctuations and discussed in detail. From the results a transition at around n=8 from a rigid constrained (n=5,6) to a softer system (n=10,12) on a molecular lenght scale was revealed with increasing alkyl chain length. A counterbalance of two competing effects of a polyethylene like behavior of the alkyl chains in the intercolumnar domains and self-organized confinement is discussed in the context of a hindered glass transition. The results were confirmed by in- and quasielastic neutron scattering
The vibrational density of states of a series of homologous triphenylene-based discotic liquid crystals HATn (n = 5, 6, 8, 10, 12) depending on the length of the aliphatic side chain is investigated by means of inelastic neutron scattering. All studied materials have a plastic crystalline phase at low temperatures, followed by a hexagonally ordered liquid crystalline phase at higher temperatures and a quasi isotropic phase at the highest temperatures. The X-ray scattering pattern for the plastic crystalline phase of all materials shows a sharp Bragg reflection corresponding to the intercolumnar distance in the lower q-range and a peak at circa 17 nm-1 related to intracolumnar distances between the cores perpendicular to the columns as well as a broad amorphous halo related to the disordered structure of the methylene groups in the side chains in the higher q-range. The intercolumnar distance increases linearly with increasing chain length for the hexagonal columnar ordered liquid crystalline phase. A similar behaviour is assumed for the plastic crystalline phase. Besides n = 8 all materials under study exhibit a Boson peak. With increasing chain length, the frequency of the Boson peak decreases and its intensity increases. This can be explained by a self-organized confinement model. The peaks for n = 10, 12 are much narrower than for n = 5, 6 which might imply the transformation from a rigid system to a softer one with increasing chain length. Moreover the results can also be discussed in the framework of a transition from an uncorrelated to a correlated disorder with increasing n where n = 8 might be speculatively considered as a transitional state.
Thermal properties and vibrational density of states of a nanoconfined discotic liquid crystal
(2014)
Neutron scattering is employed to investigate the vibrational density of states (VDOS) of the discotic liquid crystal 2,3,6,7,10,11-hexakis[hexyloxy] triphenylene (HAT6) confined to the pores of alumina oxide membranes with different pore sizes. Additionally, the phase transitions were studied by differential scanning calorimetry. The transitions were observed down to the smallest pore size. The decrease of the transition enthalpies versus inverse pore size for both transitions implies an increase of the amount of disordered amorphous material. By extrapolation of its pore size dependence, a critical pore diameter for structure formation of 17 nm is estimated. Similar to the bulk, excess contributions to the VDOS (Boson peak) are also observed for confined HAT6. The Boson peak gains in intensity and shifts to lower frequencies with decreasing pore diameter. This is discussed in the framework of a softening of HAT6 induced by the confinement due to a less-developed plastic crystalline state inside the pores compared to the bulk.
Optical polarimetry measurements of the orientational order of a discotic liquid crystal based on a pyrene derivative confined in parallelly aligned nanochannels of monolithic, mesoporous alumina, silica, and silicon as a function of temperature, channel radius (3–22 nm) and surface chemistry reveal a competition of radial and axial columnar orders. The evolution of the orientational order parameter of the confined systems is continuous, in contrast to the discontinuous transition in the bulk. For channel radii larger than 10 nm we suggest several, alternative defect structures, which are compatible both with the optical experiments on the collective molecular orientation presented here and with a translational, radial columnar order reported in previous diffraction studies. For smaller channel radii our observations can semi-quantitatively be described by a Landau–de Gennes model with a nematic shell of radially ordered columns (affected by elastic splay deformations) that coexists with an orientationally disordered, isotropic core. For these structures, the cylindrical phase boundaries are predicted to move from the channel walls to the channel centres upon cooling, and vice-versa upon heating, in accord with the pronounced cooling/heating hystereses observed and the scaling behavior of the transition temperatures with the channel diameter. The absence of experimental hints of a paranematic state is consistent with a biquadratic coupling of the splay deformations to the order parameter.
In- and quasielastic neutron scattering is employed to investigate both the vibrational density of states and the molecular dynamics of two homologous discotic liquid crystals (DLC) with different length of the alkyl side chain based on a triphenylene derivate. For both compounds characteristic low frequency excess contributions to the vibrational density of states are found. Therefore it is concluded that these liquid crystals show a glass-like behaviour. Elastic scans further show that in these materials a rich molecular dynamics takes place.
We report a high-resolution dielectric study on a pyrene-based discotic liquid crystal (DLC) in the bulk state and confined in parallel tubular nanopores of monolithic silica and alumina membranes. The positive dielectric anisotropy of the DLC molecule at low frequencies (in the quasistatic case) allows us to explore the thermotropic collective orientational order. A face-on arrangement of the molecular discs on the pore walls and a corresponding radial arrangement of the molecules is found. In contrast to the bulk, the isotropic-to-columnar transition of the confined DLC is continuous, shifts with decreasing pore diameter to lower temperatures, and exhibits a pronounced hysteresis between cooling and heating. These findings corroborate conclusions from previous neutron and x-ray-scattering experiments as well as optical birefringence measurements. Our study also indicates that the relative simple dielectric technique presented here is a quite efficient method in order to study the thermotropic orientational order of DLC-based nanocomposites.
The molecular dynamics of the triphenylene-based discotic liquid crystal HAT6 is investigated by broadband dielectric spectroscopy, advanced dynamical calorimetry and neutron scattering. Differential scanning calorimetry in combination with X-ray scattering reveals that HAT6 has a plastic crystalline phase at low temperatures, a hexagonally ordered liquid crystalline phase at higher temperatures and undergoes a clearing transition at even higher temperatures. The dielectric spectra show several relaxation processes: a localized gamma-relaxation a lower temperature and a so called alpha-2-relaxation at higher temperatures. The relaxation rates of the alpha-2-relaxation have a complex temperature dependence and bear similarities to a dynamic glass transition. The relaxation rates estimated by hyper DSC, Fast Scanning calorimetry and AC Chip calorimetry have a different temperature dependence than the dielectric alpha-2-relaxation and follows the VFT-behavior characteristic for glassy dynamics. Therefore, this process is called alpha-1-relaxation. Its relaxation rates show a similarity with that of polyethylene. For this reason, the alpha-1-relaxation is assigned to the dynamic glass transition of the alkyl chains in the intercolumnar space. Moreover, this process is not observed by dielectric spectroscopy which supports its assignment. The alpha-2-relaxation was assigned to small scale translatorial and/or small angle fluctuations of the cores.
The neutron scattering data reveal two relaxation processes. The process observed at shorter relaxation times is assigned to the methyl group rotation. The second relaxation process at longer time scales agree in the temperature dependence of its relaxation rates with that of the dielectric gamma-relaxation.
A selected series of dipole functionalized triphenylene-based discotic liquid crystals (DLCs) was synthesized and investigated in a systematic way to reveal the phase behavior and molecular dynamics. The later point is of particular importance to understand the charge transport in such systems which is the key property for their applications such as organic field-effect transistors, solar cells or as nanowires in molecular electronics, and also to tune the properties of DLCs. The mesomorphic properties were studied by polarizing optical microscopy, X-ray diffraction, and differential scanning calorimetry, which were compared to the corresponding unfunctionalized DLC. The molecular dynamics were investigated by a combination of state-of-the-art broadband dielectric spectroscopy (BDS) and advanced calorimetry such as fast scanning calorimetry (FSC) and specific heat spectroscopy (SHS). Besides localized fluctuations, surprisingly multiple glassy dynamics were detected for all materials for the first time. Glassy dynamics were proven for both processes unambiguously due to the extraordinary broad frequency range covered. The a1-process is attributed to fluctuations of the alky chains in the intercolumnar space because a polyethylene-like glassy dynamics is observed. This corresponds to a glass transition in a confined three-dimensional space. The a2-process found at temperatures lower than a1-process, is assigned to small scale rotational and/or translational in plane fluctuations of the triphenylene core inside distorted columns. This can be considered as a glass transition in a one-dimensional fluid. Therefore, obtained results are of general importance to understand the glass transition, which is an unsolved problem of condensed matter science.