Alignment behaviour of symmetrical and asymmetrical triphenylenes possessing fluoroalkylated side chains on modified substrates

The alignment behaviour of triphenylene‐based compounds possessing fluoroalkylated and alkyl side chains was investigated for the hexagonal columnar (Col_h) mesophase on polyimide‐, cetyltrimethylammonium bromide (CTAB)‐, and indium tin oxide‐coated glass substrates by polarizing optical microscopy. It was found that 2,6,10‐trinonyloxy‐3,7,11‐tris(1H,1H,2H,2H,3H,3H‐perfluorononyloxy)triphenylene and 2,6,11‐trinonyloxy‐3,7,10‐tris(1H,1H,2H,2H,3H,3H‐perfluorononyloxy)triphenylene exhibit spontaneous homeotropic alignment on these substrates. On the other hand, it was found that 2,6,10‐triheptyloxy‐3,7,11‐tris(1H,1H,2H,2H,3H,3H‐perfluoroheptyloxy)triphenylene, 2,6,11‐triheptyloxy‐3,7,10‐tris(1H,1H,2H,2H,3H,3H‐perfluoroheptyloxy)triphenylene, 2,6,10‐trihexyloxy‐3,7,11‐tris(1H,1H,2H,2H,3H,3H‐perfluorohexyloxy)triphenylene, 2,6,11‐trihexyloxy‐3,7,10‐tris(1H,1H,2H,2H,3H,3H‐perfluorohexyloxy)triphenylene, 2,6,10‐tributyloxy‐3,7,11‐tris(1H,1H,2H,2H,3H,3H‐perfluorobutyloxy)triphenylene and 2,6,11‐tributyloxy‐3,7,10‐tris(1H,1H,2H,2H,3H,3H‐perfluorobutyloxy)triphenylene do not show such spontaneous homeotropic alignment on these substrates. These results indicate that the spontaneous homeotropic alignment of the Col_h phase could be easily attained by the introduction of an appropriate length of the fluoromethylene chains in the peripheral parts of discogens. Therefore, it is suggested that the balance between the hydrocarbon part including the triphenylene core and the fluoroalkyl part determines the alignment control behaviour. Furthermore, it was found that alignment behaviour is independent of the rotation symmetry of the chemical structure but is dependent on the number of fluoromethylene chains in the chemical structure.     

苯并菲盘状液晶的合成、亲氟效应及分子对称性对介晶性的影响

New symmetrical and asymmetrical triphenylene-containing discotic liquid crystals with two different peripheral alkyl chains, known as sym-TP(OC6H13)3(OR)3 and asym-TP(OC6H13)3(OR)3, were synthesized. Their thermotropic liquid crystal properties were investigated through polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analyses. The asyrranetdcal discogens are 2,6,11-rialkoxy-3,7,10-trihexyloxytriphenylenes, with the alkyl chain carbon numbers varying from 3-10, 12, and 14, while the symmetrical compounds are 2,6,10-trialkyloxy-3,7,11-trihexyloxytriphenylene. Two fluoroalkoxy substituted triphenylene discogens, 2,6,10-td(4,4,4-trifluorobutoxy)-3,7,11-trihexyloxytriphenylene and its asymmetrical isomer 2,6,11-tri(4,4,4-trifluorobutoxy)-3,7,10-trihexyloxytdphenylene were prepared. These two compounds show higher melting and clearing points than their alkoxy analogs, which implies that fluorophilic effect exists in the formation and stabilization of discotic columnar mesophase. The triphenylene derivatives TP(OC6H13)3(OR)3 with two different peripheral chains, symmetrically or asymmetrically attached on triphenylene cores, have lower melting points and clearing points than those of the higher symmetrical compounds TP(OR)6 with the same total chain carbon numbers. The mixed-chain-triphenylenes with longer alkoxy chains (n=9,10,12,14) show columnarmesophase at room temperature.     

2,6,10-Tris(dianisylaminium)-3,7,11- tris(hexyloxy)triphenylene: a robust quartet molecule at room temperature

[reaction: see text] A new triradical molecule, 2,6,10-tris(dianisylaminium)-3,7,11-tris(hexyloxy)triphenylene 1(3+), was synthesized by oxidative trimerization, palladium-catalyzed amination, and subsequent oxidation. It was chemically stable with a half-life > 1 month and displayed the magnetic parameter of S = 3/2 even at room temperature.     

Synthesis of Mixed Tail Triphenylene Discotic Liquid Crystals： Molecular Symmetry and Oxygen-Atom Effect on the Stabilization of Columnar Mesophases

Small change in chemical structure of discotic liquid crystals can cause big difference in their mesomorphism. Replacing of the alkoxy peripheral chains of triphenylene by oxygen-atom containing ester chains would result in novel mesomorphism. A series of mixed tail triphenylenes containing propoxyacetyloxy and alkoxy, abbreviated as C18H6（OCnH2n＋1）3（OCOCH2OC3H7）3, n=4-8, and hexa（propyloxyacetyloxy）triphenylene, C18H6（OCOCH2OC3H7）6 were synthesized. Thermal gravimetry analysis （TGA） of three discogens showed that they had good thermal stability till 350 ℃. The mesomorphism was investigated through differential scanning calorimetry （DSC） and polarized optical microscopy （POM）. The preliminary X-ray diffraction （XRD） results of one compound showed that it exhibited ordered hexagonal columnar （Colho） mesophase. These mixed tail triphenylene derivatives possessed much stable Colho mesophase and wider mesophase ranges than their hexaalkoxytriphenylene C18H6（OR）6 and hexaalkanoyloxytriphenylene C18H6（OCOR＇）6 analogues. The asymmetrical compounds 2,6,11-trialkoxy-3,7,10-tri（2-propyloxyacetyloxy）triphenylenes with n=5-8 displayed higher clearing points and wider temperature ranges than their symmetrical isomers 2,6,10-trialkoxy-3,7,11-tri（2-propyloxyacetyloxy）- triphenylenes, while C18H6（OCOCH2OC3H7）6 had the highest clearing point due to the β-oxygen-atom effect.     

Alignment behavior for novel triphenylene compounds possessing fluoroalkylated side chains on modified substrates

The alignment behavior of the triphenylene compounds possessing fluoroalkylated side chains was investigated for the hexagonal columnar (Col_h) mesophase on the polyimide-, cetyltrimethylammonium bromide (CTAB)-, and indium-SnO₂ (ITO)-coated glass substrates by polarizing optical microscopy. It was found that 2,3,6,7,10,11-hexakis(1H,1H,2H,2H,3H,3H-perfluoroheptyloxy)- and 2,3,6,7,10,11-hexakis(1H,1H,2H,2H,3H,3H-perfluorononyloxy)-triphenylenes exhibit a spontaneous homeotropic alignment on these substrates, in contrast to the non-uniformity of alignment of Col_h phase in the corresponding hydrocarbon mesogens. On the other hand, it was also found that 4,4,4-trifluorobutyloxy, 4,4,5,5,5-pentafluoropentyloxy and 4,4,5,5,6,6,6-heptafluorohexyloxy derivatives do not show such a spontaneous homeotropic alignment on these substrates. These results indicate that the spontaneous homeotropic alignment of the Col_h phase could be easily attained by the introduction of an appropriate number and length of the fluoromethylene chains in the peripheral parts of discogens.     

Helical arrangement of a hydrogen‐bonded columnar liquid crystal induced by a centered triphenylene derivative bearing chiral side‐chains

A hydrogen‐bonded helical columnar liquid crystal was synthesized, in which the helical structure is induced by a centered triphenylene derivative bearing chiral side‐chains. The triphenylene derivative, 2,6,10‐tris(carboxymethoxy)‐3,7,11‐tris((S)‐(‐)‐2‐methyl‐1‐butanoxy)triphenylene ( TPC4(S) ), and a dendric amphiphile, 3,5‐bis‐(3,4‐bis‐dodecyloxy‐benzyloxy)‐N‐pyridine‐4‐yl‐benzamide ( DenC12 ), were mixed in a 1:3 ratio to obtain a complex, TPC4(S)‐DenC12 . Analyses by ¹H‐NMR spectroscopy, diffusion ordered spectroscopy (DOSY), CD spectroscopy, infrared (IR) spectroscopy, polarized optical microscopy (POM), differential scanning calorimetry (DSC), and X‐ray diffractometry revealed that TPC4(S)‐DenC12 self‐assembles to form helical columnar stacks in solution and a helical columnar liquid crystal in bulk. The hydrogen bonding between TPC4(S) and DenC12 is essential for the helical columnar organization, and the preference for a one‐handed helical conformation is likely derived from the steric interaction between the chiral side‐chains and the dendric amphiphiles in the packing of the hydrogen‐bonded columnar assemblies. Copyright © 2008 John Wiley & Sons, Ltd.     

Alignment behaviour of the discotic nematic phase of 2,3,6,7,10,11-hexa(4-n-octyloxybenzoyloxy)triphenylene on polyimide and cetyltrimethylammonium bromide coated substrates

The orientational behaviour of the nematic discotic phase of 2,3,6,7,10,11-hexa(4-n-octyloxybenzoyloxy)triphenylene (C8OBT) on substrates coated with a polyimide or cetyltrimethylammonium bromide (CTAB) was investigated by polarizing optical microscopy. The averaged order parameters and directions of the triphenylene core and the carbonyl groups of C8OBT were evaluated by an infrared dichroic method. The discotic nematic (N_D) phase of C8OBT exhibits a homeotropic alignment on a polyimide film, a typical nematic schlieren texture on a glass substrate, and a tilted or planar homogeneous alignment on a CTAB-coated substrate. The order parameter of the triphenylene core is higher on a polyimide film (S = 0.6) than on a CTAB-coated substrate (S = 0.2), whereas that of the carbonyl groups remains roughly constant at 0.2 to 0.3 independent of the substrate for the N_D phase.     

Design of discotic liquid crystal enabling complete switching along with memory of homeotropic and homogeneous alignment over a large area

The alignment control of discotic columnar liquid crystals (LCs), featuring a low motility of the constituent molecules and thus having a large viscosity, is a challenging task. Here we show that triphenylene hexacarboxylic ester, when functionalized with hybrid side chains consisting of alkyl and perfluoroalkyl groups in an appropriate ratio, gives a hexagonal columnar (Col_h) LC capable of selectively forming large-area uniform homeotropic or homogeneous alignments, upon cooling from its isotropic melt or upon application of a shear force at its LC temperature, respectively. In addition to the alignment switching ability, each alignment state remains persistent unless the LC is heated to its melting temperature. In situ X-ray diffraction analysis under the application of a shear force, together with polarized optical microscopy observations, revealed how the columnar assembly is changed during the alignment-switching process. The remarkable behavior of the discotic LC is discussed in terms of its rheological properties.

A columnar liquid crystal consisting of a triphenylene hexacarboxylic ester mesogen and semifluoroalkyl side chains shows complete switching between homeotropic and homogeneous alignments, each of which remains persistent up to its melting point.     

Alignment behaviour of the discotic nematic phase of 2,3,6,7,10,11-hexa(4-n-octyloxybenzoyloxy)triphenylene on polyimide and cetyltrimethylammonium bromide coated substrates

The orientational behaviour of the nematic discotic phase of 2,3,6,7,10,11-hexa(4-n-octyloxybenzoyloxy)triphenylene (C8OBT) on substrates coated with a polyimide or cetyltrimethylammonium bromide (CTAB) was investigated by polarizing optical microscopy. The averaged order parameters and directions of the triphenylene core and the carbonyl groups of C8OBT were evaluated by an infrared dichroic method. The discotic nematic (N_D) phase of C8OBT exhibits a homeotropic alignment on a polyimide film, a typical nematic schlieren texture on a glass substrate, and a tilted or planar homogeneous alignment on a CTAB-coated substrate. The order parameter of the triphenylene core is higher on a polyimide film (S = 0.6) than on a CTAB-coated substrate (S = 0.2), whereas that of the carbonyl groups remains roughly constant at 0.2 to 0.3 independent of the substrate for the N_D phase.     

Surfactants having polyfluoroalkyl chains. II. Syntheses of anionic surfactants having two polyfluoroalkyl chains including a trifluoromethyl group at each tail and their flocculation-redispersion ability for dispersed magnetite particles in water

Anionic surfactants having two polyfluoroalkyl chains per molecule, i.e. the sodium salt of bis(1H, 1H, 2H,2H-heptadeca-fluorodecyl)-2-sulfosuccinate, CF₃(CF₂)₇(CH₂)₂OCOCH₂CH(SO₃Na)COO(CH₂)₂(CF₂)₇CF₃, the sodium salt of bis(1H, 1H, 2H, 2H-tridecafluoro-octyl)-2-sulfosuccinate, CF₃(CF₂)₅(CH₂)₂OCOCH₂CH(SO₃Na)COO(CH₂)₂(CF₂)₅CF₃, and the sodium salt of bis(1H, 1H, 2H, 2H-nonafluorohexyl)-2-sulfosuccinate, CF₃(CF₂)₃(CH₂)₂OCOCH₂CH(SO₃Na)COO(CH₂)₂(CF₂)₃CF₃, have been prepared from maleic anhydride, the corresponding alcohols possessing a polyfluoroalkyl chain and sodium hydrogen sulfite. The flocculation and redispersion abilities of these surfactants for dispersed magnetic particles in water have been examined to investigate the effect of the chain length. It was found that this ability was enhanced by an increase in the chain length. The contact angles for water for pelleted surface-modified magnetite have been measured. In order to compare this ability and the contact angles, data for other fluorinated surfactant have been obtained. The Kraff point, the surface tension and the pNa of the aqueous surfactant solutions have also been measured.     

Collective and molecular processes in a new class of ferroelectric liquid crystals

Electro-optic and dielectric studies have been performed for a thioester (with a chiral chain incorporating the lactic acid ester moiety), which exhibits a monotropic room temperature ferroelectric S_c* phase. Moreover, there are some hints that this substance also shows the recently discovered helicoidal S_A* phase. The dielectric and electro-optic measurements have been carried out using ITO coated glass plates (d = 10 μm). Planar alignment was obtained by means of an AC electric field (v = 1Hz and V_p-p = 70V). The tilt angle and spontaneous polarization temperature dependences show that the S_A*-S_c* transition is of second order. Soft mode behaviour in the pretransitional region also confirms this result. The monotropic S_c* phase exhibits a rather strong Goldstone mode (GM) with pronounced temperature dependence of the dielectric parameters. The molecular reorientation about the long axis has been found for both principal alignments. The homeotropic effective alignment was obtained by applying a magnetic field of 1-2 T to a thick sample (c. 100μm) placed in a specially designed cell for anisotropic high frequency measurements. The reorientation about the long axis gives a broad spectrum centred at c. 100MHz. This spectrum shows minor changes at the S_A*-S_c* transition.     

Influence of molecular mass on the liquid crystal alignment of photosensitive fluorinated polyester films

Photosensitive fluorinated polyesters (polymer-n) of varying molecular mass M _n (number-average molecular mass) were synthesized. The thin films formed from polymer-n samples could induce liquid crystal (LC) alignment after irradiation by linearly polarized ultraviolet light. The LC alignment direction on the irradiated films was investigated in detail by linearly polarized infrared spectroscopy and polarizing optical microscopy. It was found that LC alignment behaviour changed with change in the molecular mass of polymer-n: irradiated films with lower or higher M _n induced homeotropic or homogenous alignment, respectively. There was no clear morphological anisotropy in these aligned films, as observed by atomic force microscopy. The surface energies of the irradiated films were also measured using the indirect contact angle method, where both surface energy and its polar component increased with increasing M _n. The variation in M _n could be considered as a main reason for varying alignment behaviour.     

Crystallographic and ab initio theoretical studies of (2R,3R)-1-methyl-5-oxo-2-phenyltetrahydro-1H-pyrrole-3-carboxylic acid. The comparison of chiral (I) and racemic (II) structure

Crystal and molecular structures of (2R,3R)-1-methyl-5-oxo-2-phenyltetrahydro-1H-pyrrole-3-carboxylic acid (I) and (2R^*,3R^*)-1-methyl-5-oxo-2-phenyltetrahydro-1H-pyrrole-3-carboxylic acid (II) are presented. The alternative packings were studied using ab initio quantum-chemical methods. Energies of hydrogen bonds for real and model cases are discussed. Infinite chains of molecules instead of carboxylic acid dimers were observed.     

Mesomorphic phase transition behavior of novel triphenylene compounds possessing fluoroalkylated side chains

This report discusses the effect of fluoroalkyl chain on the mesomorphism. Several homologues of novel triphenylene compounds possessing fluoroalkylated side chains were synthesized. Studies of X-ray diffraction, DSC and texture observations by polarized microscope revealed that these homologues show hexagonal columnar (Col_h) mesophase. These homologues made columnar mesophase stabilize and the melting point increase, as compared with corresponding alkyloxytriphenylenes. In the case of fluoroalkyloxytriphenylenes possessing fluoromethylene side chains, the increase of the fluoromethylene chain length stabilized columnar mesophase, made the phase transition enthalpy (Col_h-Iso) and entropy (Col_h-Iso) increase. It is considered that these results are due to the fluorophilic interaction, and that the fluorophilic interaction is important for stabilizing columnar mesophase.     

Polar and azimuthal alignment of a nematic liquid crystal by alkylsilane self-assembled monolayers: effects of chain-length and mechanical rubbing

Alkylsilane self-assembled monolayers (SAMs) on oxide substrates are commonly used as liquid crystal (LC) alignment layers. We have studied the effects of alkyl chain length, photolytic degradation, and mechanical rubbing on polar and azimuthal LC anchoring. Both gradient surfaces (fabricated using photolytic degradation of C18 SAMs) and unirradiated SAMs composed of short alkyl chains show abrupt transitions from homeotropic to tilted alignment as a function of degradation or chain length. In both cases, the transition from homeotropic to tilted anchoring corresponds to increasing wettability of the SAM surfaces. However, there is an offset in the critical contact angle for the transition on gradient vs unirradiated SAMs, suggesting that layer thickness is more relevant than wettability for LC alignment. Mechanical rubbing can induce azimuthal alignment along the rubbing direction for alignment layers sufficiently near the homeotropic-to-planar transition. Notably, mechanical rubbing causes a small but significant shift in the homeotropic-to-tilted transition, e.g., unrubbed C5 SAMs induce homeotropic anchoring, but the same surface after rubbing induces LC pretilt.     

Patterned alignment of nematic liquid crystals generated by inkjet printing of gold nanoparticles and emissive carbon dots on both flexible polymer and rigid glass substrates

Patterned homeotropic alignment using nanoparticles (NPs) was achieved using inkjet printing. Two types of gold NPs, one smaller and one larger in core diameter (2 and 5 nm) capped with a monolayer of dodecanethiol, and emissive carbon dots with a core diameter of 2.5 nm featuring a mixed ligand shell of carboxylic acid groups and aliphatic hydrocarbon chains were tested on both rigid glass and flexible polycarbonate substrates. To define the director across the entire cell and not just in the NP-printed areas, alignment ‘underlayers’ were tested, and 30° obliquely evaporated SiO_x as alignment ‘underlayer’ generally provided the best results with the highest quality of the homeotropic alignment as well as the best contrast at the boundary between printed and non-printed (i.e. homeotropic and planar) domains of the fabricated cells. We also report that the chemical nature of the nematic liquid crystal (LC) used, the number of layers printed and the composition of the nano-ink need to be adjusted to obtain pattern alignment devices that positively benefit from both the properties of the LC and the nanomaterial printed.     

Morphological phase behaviour under pressure of polycatenar mesogens with a perfluorinated moiety

Two polycatenar materials composed of a four-aromatic-ring core with a perfluorinated moiety attached in one terminal position through either butylene- or pentylene spacer groups, and three tetradecyloxy chains at the other end (abbreviated as 14PC₄F and 14PC₅F), were investigated to study the effect of pressure on the phase transition behaviour. A polarizing optical microscope equipped with a high pressure optical hot stage, was used for the purpose. The T vs. P phase diagrams of 14PC₄F and 14PC₅F were constructed in the pressure region up to 100 MPa. 14PC₄F showed the stable crystal (Cr₁)-columnar tetragonal (Col_tet)-smectic A (SmA)-columnar hexagonal (Col_h)-isoropic liquid (I) phase transition sequence under all pressures. 14PC₅F exhibited the phase sequence metastable crystal (Cr₂)-cubic (Cub)-Col_tet-SmA-I in a melt-cooled sample on heating under pressure. But when the melt-cooled Cr₂ sample was annealed at 52-54°C for 2-3 h, the stable crystal (Cr₁) was formed slowly, giving a stable Cr₁-Cub-Col_tet-SmA-I phase sequence. The temperature region of the stable cubic phase broadened with increasing pressure. Furthermore a new mesophase of 14PC₅F was pressure-induced between the I and SmA phases on cooling at pressures above about 16 MPa. Since the monotropic mesophase exhibited a texture very similar to that of the high temperature Col_h phase of 14PC₄F with planar orientation, the new phase was assigned at a high temperature columnar hexagonal phase of 14PC₅F.     

Anomalous relaxation of a twisted cell under an external magnetic field: The nearly homogeneous relaxation

We report experimental and theoretical investigations of the dynamic behaviour of a π/2 twisted NLC layer in a magnetic field. When a magnetic field H is applied in the layer plane at a suitable angle β with respect to the easy axis on the first surface, the relaxation towards the equilibrium texture occurs through a slow decay of unstable textures. Depending on the values of H and β, the relaxation of the system can be nearly homogeneous or strongly inhomogeneous. In this paper we restrict our attention to the case where the relaxation occurs in a nearly homogeneous way. The theoretical relaxation time τw of the unstable textures is found to depend strongly on the angle β and on the amplitude of the magnetic field. The experimental dependence of τw on H and β is found to be in good agreement with the theoretical predictions. The relaxation process is extremely sensitive to small dishomogeneities of the director easy alignment on the surfaces. From the measured relaxation we are able to estimate a spread of 0.3° on the surface easy axes at a planar anchored SiO surface.     

Study of the alkylation of chlorosilanes. Part I. Synthesis of tetra(1H, 1H, 2H, 2H-polyfluoroalkyl)silanes

The synthesis and structural characterization of tetra(1H, 1H, 2H, 2H-polyfluoroalkyl)silaneswith the same or different chain lengths C_nF_2n+1 linked to Si (1n6) is reported.

When the synthesis was effected from chlorosilanes and fluorinated organomagnesiumor organolithium reagents, the trialkylsilanes were obtained. The last fluorinated chainwas introduced either via a fluoroalkyllithium reagent or by hydrosilylation of thetrialkylsilanes.

Some properties and characterization by ¹H, ¹⁹F and ²⁹Si NMR spectroscopy of the1H, 1H, 2H, 2H-polyfluoroalkylsilanes are described.     

Ab initio study of the tautomeric forms of some quinolinediones

7,8-dihydroquinoline-4,5 (1H,6H)-dione (1) and 7,8-dihydroquinoline-2,5-(1H,6H)-dione (2) in their tautomeric oxo and hydroxy forms have been studied by ab initio Hartree-Fock calculations; tautomerization energies predict a more stable hydroxy structure having an intramolecular hydrogen bond for compound 1, whereas the oxo form is slightly-preferred for compound 2. Fourier Transform-Infra Red (FT-IR) spectra in CHCl₃ solution indicate that the predicted most stable tautomers in the vapour phase remain as such.