Ether- and Thioether-Linked Naphthalene-Based Liquid-Crystal Dimers: Influence of Chalcogen Linkage and Mesogenic-Arm Symmetry on the Incidence and Stability of the Twist–Bend Nematic Phase

The twist–bend nematic (N_TB) phase with a heliconical nanostructure of the local director generating symmetry breaking by achiral bent-shaped molecules is a hot topic of current liquid-crystal science. As opposed to the most common methylene-linked dimers, this study demonstrates chalcogen ether- and/or thioether-linked 6-(4-cyanophenyl)-2-naphthyl-based liquid-crystal dimers with symmetric and asymmetric π-conjugated mesogenic-arm structures that exhibit the N_TB phase. Although the symmetric bis(ether)-linked dimer exhibits only the conventional nematic (N) phase, the asymmetric bis(ether)-linked dimer can form the N_TB phase. All thioether-linked dimers form the N_TB phase, wherein the dimers with asymmetric arms vitrify in the N_TB phase on cooling to room temperature. The phase transitions are discussed in terms of the chalcogen linkage combination, mesogenic-arm symmetry, and spacer length. It is revealed that thioether-linked dimers based on asymmetric π-conjugated mesogenic arms with terminal cyano groups are highly beneficial for the realization of materials that form a wide range of N_TB phases and glassy N_TB states at room temperature.     

Azobenzene-based liquid crystal dimers and the twist-bend nematic phase

ABSTRACT

The synthesis and characterisation of two new sets of non-symmetric liquid crystal dimers is reported, the 1-(4-substitutedazobenzene-4′-yloxy)-6-(4-cyanobiphenyl-4′-yl)hexanes (CB6OABX) and 1-(4-substitutedazobenzene-4′-yloxy)-6-(4-cyanobiphenyl-4′-yloxy)pentanes (CBO5OABX). The terminal substituents are methyl, methoxy, butyl, butyloxy, nitrile and nitro. All the CB6OABX dimers exhibit twist-bend nematic (N_TB) and nematic (N) phases. The CBO5OABX dimers also all show an N phase but only the butyl and butyloxy homologues exhibit the N_TB phase. The transitional behaviour of the non-symmetric dimers is compared to that of the corresponding symmetric dimers, the 1,5-bis(4-substitutedazobenzene-4′-yloxy)pentanes (XABO5OABX) and either 1,7-bis(4-cyanobiphenyl-4′-yl)heptane or 1,5-bis(4-cyanobiphenyl-4′-yloxy)pentane. The XABO5OABX dimers all show a nematic phase and in addition, the butyl homologue exhibits a smectic A phase. The difference in transitional behaviour between the CB6OABX and CBO5OABX dimers is attributed to the difference in their molecular shapes arising from different bond angles between the para axis of the cyanobiphenyl unit and the first bond in the spacer. Specifically, the all-trans conformation of a CBO5OABX dimer is more linear than that of the corresponding CB6OABX dimer. Differences within each set of dimers are attributed to changes in the average molecular shape and the strength of the mixed mesogen interaction on varying the terminal group. Crystal structures are reported for CB6OABOMe, CBO5OABNO₂ and MeOABO5OABOMe.     

Synthesis and characterisation of thermotropic liquid-crystalline properties of azomethine dimers

A series of azomethine dimers were prepared by condensation reactions of benzaldehyde, biphenylcarboxaldehyde and 9-anthraldehyde with various aromatic diamines of varying flexibility in ethanol in the presence of tosic acid. Their chemical structures were determined by Fourier transform infrared and ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopies, as well as elemental analysis. Their thermal properties were also examined by using a number of experimental techniques, including differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), polarising optical microscopy (POM) and variable temperature X-ray diffraction (VTXRD). Azomethine dimer, prepared from benzaldehyde and 1,9-bis(4-aminophenoxy)nonane, exhibited a monotropic, nematic liquid-crystalline (LC) phase. The majority of the azomethine dimers containing biphenyl moieties exhibited enantiotropic, nematic LC phase on melting at relatively low temperatures, since they developed typical Schlieren, threaded or marbled textures in their LC phase. They also had accessible isotropisation temperatures well below their decomposition temperatures. Azomethine dimers containing anthracene moieties did not exhibit LC properties, but exhibited polymorphism as determined by POM and VTXRD in two cases. All of these azomethine dimers in the series had excellent thermal stability that was in the broad range of temperatures of 307–400°C depending on their degrees of aromaticity index.     

Why do non-symmetric dimers intercalate? The synthesis and characterisation of the α-(4-benzylidene-substituted-aniline-4′-oxy)-ω-(2-methylbutyl-4′-(4″-phenyl)benzoateoxy)alkanes

Ten new non-symmetric liquid crystal dimers belonging to the family of compounds α-(4-benzylidene-substituted-aniline-4′-oxy)-ω-(2-methylbutyl-4′-(4″-phenyl)benzoateoxy)-alkanes have been synthesised and their transitional properties characterised. The dimers contain either a hexamethylene or octamethylene spacer, while the terminal substituents on the 4-benzylideneaniline fragment are H, CH₃, F, Cl and Br. The unsubstituted dimers are not liquid crystalline, while the remaining compounds exhibit enantiotropic nematic behaviour. The trends in the clearing temperatures, according to the chemical nature of the terminal substituent, are largely consistent with those established for conventional low molar mass liquid crystals. Three of the dimers also exhibit an intercalated smectic A phase, specifically the two bromo-substituted dimers and the chloro-substituted dimer containing a hexamethylene spacer. The driving force for the formation of this phase is considered to be, at least in part, the specific anisotropic interaction between the unlike mesogenic units. The absence of smectic behaviour for the isosteric methyl-substituted dimers reveals that steric factors alone cannot stabilise the intercalated smectic A phase.     

On the twist-bend nematic phase formed directly from the isotropic phase

The intriguing twist-bend nematic (N_TB) phase is formed, primarily, by liquid crystal dimers having odd spacers. Typically, the phase is preceded by a nematic (N) phase via a weak first-order transition. Our aim is to obtain dimers where the N_TB phase is formed directly from the isotropic (I) phase via a strong first-order phase transition. The analogy between such behaviour and that of the smectic A (SmA)–N–I sequence suggests that this new dimer will require a short spacer. This expectation is consistent with the prediction of a molecular field theory, since the decrease in the spacer length results in an increase in the molecular curvature. A vector of odd dimers based on benzoyloxybenzylidene mesogenic groups with terminal ethoxy groups has been synthesised with spacers composed of odd numbers of methylene groups. Spacers having 5, 7, 9 and 11 methylene groups are found to possess the conventional phase sequence N_TB–N–I; surprisingly, for the propane spacer, the N_TB phase is formed directly from the I phase. The properties of these dimers have been studied with care to ensure that the identification of the N_TB phase is reliable.     

Fluorescent Short-Stranded Helical Foldamers Based on L-shaped Dibenzopyrrolo[1,2-a][1,8]naphthyridine

Helical structures were constructed by using π-spacer-bridged dimers of dibenzopyrrolo[1,2-a][1,8]naphthyridine, which has a highly fluorescent L-shaped π-extended skeleton. Three dimers with biphenylene (dimer 1 ), phenanthrene (dimer 2 ), and m-phenylene (dimer 3 ) spacers, as well as a fixed-helical dimer 4 where two quinolone rings were covalently cross-linked, were designed and prepared. ¹H NMR and ROESY spectra revealed that dimers 1 and 2 adopted helical forms in solution, whereas dimer 3 did not. The helical conformation of 1 was strengthened by addition of either polar or nonpolar solvents to the chloroform solution, which suggested that π–π stacking was the main contributor to the stabilization of the helical structure. All of the dimers, including fixed-helical dimer 4 , emitted fluorescence with high quantum yields (ϕ=0.79–0.86).     

Facile Synthesis of Liquid Crystal Dimers Bridged with a Phosphonic Group

Liquid crystal (LC) dimers with well-defined composition and structure arouse broad attentions for their exhibiting LC properties beyond conventional low molar mass mesogens and serving as fascinating model compounds for LC polymers. Here in this work, a series of LC dimers bridged with a phosphonic group have been synthesized through a facile free radical mediated addition reaction between hypophosphorous acid and vinyl terminated cyanobiphenyl mesogens with variant length alkyl spacers. In addition, two esterified derivatives and a group of mono-addition homologues with a terminal phosphonic acid group have also been prepared for comparison study. All the newly synthesized compounds exhibit monotropic nematic (N) phase with typical schlieren textures except for the LC dimer with the longest eleven-methylene spacer, which surprisingly shows twist-bend nematic (N_TB) phase directly from the isotropic state upon cooling. Moreover, the thermal transition properties such as the nematic-isotropic transition temperatures and associated entropy changes of the series LC dimers display a modest odd-even effect. Furthermore, both the LC dimers and the mono-addition homologues in N phase are quite easy to achieve homeotropic alignment upon annealing thanks to the supramolecular interactions between the introduced phosphonic acid group and the hydroxylated glass surface. This work thus provides a novel synthesis strategy for a class of LC materials bridged with a phosphonic acid group prone to further functionalization, which may serve as promising vertical alignment agents and pave the way for developing a new kind of functionalized LC materials of N_TB phase.     

Liquid crystal dimers derived from naturally occurring chiral moieties: synthesis and characterization

Naturally occurring cholesterol and α-chloroalkanoyl units derived from natural α-amino acids (l-valine, l-leucine, and l-isoleucine) have been utilized to prepare three different series of nonsymmetric liquid crystal dimers. Tolane (diphenylacetylene), which is known to possess several promising structural features, has been chosen as the other mesogenic segment to covalently tether with cholesterol through a flexible spacer. In each series, the terminal α-chloro ester group attached to the tolane unit is kept constant, while the length and parity of the spacer have been varied; specifically, three dimers comprising even-parity spacer of varying length, and one compound with an odd-parity spacer constituted a series. The phase behavior of these dimers has been ascertained mainly by polarizing microscopic and calorimetric studies. Except one, all the 11 dimers display enantiotropic mesomorphism. Within the series, clearing temperatures exhibit a dramatic odd-even effect wherein the even-parity dimers possess higher values. In general, the dimers comprising α-chloro ester group derived from l-valine and l-leucine stabilize chiral nematic and/or smectic phase/s, while the compounds with terminal group resulting from l-isoleucine show twist grain boundary phase additionally; this implies that the nature of the α-chloro ester group influences the phase behavior. Notably, an odd-parity dimer with an α-chloro ester group derived from l-valine exhibits a transition from an intercalated smectic A phase to a monolayer (unknown) smectic phase, as evidenced by optical, calorimetric, and X-ray diffraction studies. As representative case, a dimer has been screened for antimicrobial activity by disc diffusion method; a notable activity has been found against some microbes.     

A computer simulation of model discotic dimers

We set up a model for discotic liquid crystal dimers and study, by means of Monte Carlo simulations, their phase behaviour and self–assembling properties, in comparison with the simpler monomeric case. Each discotic dimer is described by two oblate Gay–Berne ellipsoids connected by a flexible spacer, modelled by a harmonic “spring” of three different lengths. We find that dimerization in general yields produces a significant change on the phase behaviour, with an increase of the columnar–nematic transition temperature, a widening of the nematic region and the apparent suppression of the crystalline phase in favour of the columnar phase up to very low temperatures. Longer spacers prove to ease the formation of columns and to increase the orientational order. Contribution to the Fernando Bernardi memorial issue.     

Impact of configuration and fluorination on the solubility of octyl ester benzoate dimers in CO2

Data are reported on the phase behavior of hydrocarbon and semifluoroinated octyl ester benzoate dimers in CO₂ to temperatures of 100 °C and pressures of 1 600 bar. The experimental data at 75 °C demonstrate that the non-fluorinated head-to-head (H–H) dimer dissolves in CO₂ at ∼400 bar lower pressures than the non-fluorinated tail-to-tail (T–T) dimer. Even though partially fluorinating the octyl tails of the H–H and T–T dimers renders them soluble in CO₂ at pressures near 200 bar, it still takes ∼40 bar more pressure to dissolve the fluorinated T–T dimer as compared to the H–H dimer. The difference in pressures needed to dissolve these dimers is attributed to steric constraints on the coplanarity of the benzene rings imposed by the H–H regiochemistry that do not exist with T–T dimers. Semi-empirical quantum mechanics calculations suggest that the H–H dimer has a twisted, non-coplanar conformation due to the steric effect of the octyl ester groups while the T–T dimer has a less twisted conformation. Steric hindrance in the H–H dimer reduces considerably resonance or conjugation between the π electrons of the aromatic groups which also reduces the dipole moments of the H–H dimers compared to those of the T–T dimers.     

Self-propelled nanodimer bound state pairs

A pair of chemically powered self-propelled nanodimers can exist in a variety of bound and unbound states after undergoing a collision. In addition to independently moving unbound dimers, bound Brownian dimer pairs, whose center-of-mass exhibits diffusive motion, self-propelled moving dimer pairs with directed motion, and bound rotating dimer pairs, were observed. The bound pairs arise from a solvent depletion interaction, which depends on the nonequilibrium concentration field in the vicinity of dimers. The phase diagram reported in the paper shows regions in monomer interaction energy-diameter plane where these bound and unbound states are found. Particle-based simulations and analytical calculations are used to provide insight into the nature of interaction between dimers that gives rise to the observed bound states.     

Vibrational dynamics of carboxylic acid dimers in gas and dilute solution

Ultrafast mid-IR transient absorption spectroscopy has been used to study the vibrational dynamics of hydrogen-bonded cyclic dimers of trifluoroacetic acid and formic acid in both the gas and solution phases (0.05 M in CCl(4)). Ultrafast excitation of the broad O-H cyclic dimer band leads, in the gas phase, to large-scale structural changes of the dimer creating a species with a distinct free O-H stretching band on 20 ps and 200 ps timescales. These timescales are assigned to ring-opening and dissociation of the dimer, respectively. In the solution phase, no such structural rearrangement occurs and our results are consistent with previous studies. The gas phase dynamics are insensitive to both the specific excitation energy (over a span of 550 cm(-1)) and the chemical identity of the dimer.     

Optically Biaxial,Re‐entrant and Frustrated Mesophases in Chiral,Non‐symmetric Liquid Crystal Dimers and Binary Mixtures

Sixteen optically active, non‐symmetric dimers, in which cyanobiphenyl and salicylaldimine mesogens are interlinked by a flexible spacer, were synthesized and characterized. While the terminal chiral tail, in the form of either (R)‐2‐octyloxy or (S)‐2‐octyloxy chain attached to salicylaldimine core, was held constant, the number of methylene units in the spacer was varied from 3 to 10 affording eight pairs of (R & S) enantiomers. They were probed for their thermal properties with the aid of orthoscopy, conoscopy, differential scanning calorimetry and X‐ray powder diffraction. In addition, the binary mixture study was carried out using chiral and achiral dimers with the intensions of stabilizing optically biaxial phase/s, re‐entrant phases and important phase sequences. Notably, one of the chiral dimers as well as some mixtures exhibited a biaxial smectic A (SmA_b) phase appearing between a uniaxial SmA and a re‐entrant uniaxial SmA phases. The mesophases such as chiral nematic (N*) and frustrated phases viz., blue phases (BPs) and twist grain boundary (TGB) phases, were also found to occur in most of the dimers and mixtures. X‐ray diffraction studies revealed that the dimers possessing oxybutoxy and oxypentoxy spacers show interdigitated (SmA_d) phase where smectic periodicity is over 1.4 times the molecular length; whereas in the intercalated SmA (SmA_c) phase formed by a dimer having oxydecoxy spacer the periodicity was found to be approximately half the molecular length. The handedness of the helical structure of the N* phases formed by two enantiomers was examined with the aid of CD measurements; as expected, these enantiomers showed optical activities of equal magnitudes but with opposite signs. Overall, it appears that the chiral dimers and mixtures presented herein may serve as model systems in design and developing novel materials exhibiting the apolar SmA_b phase possessing D_2h symmetry and nematic‐type biaxiality.     

W-shaped mesogens and variations of their molecular structure

New bent-core liquid crystalline dimers with W-shaped molecular geometry have been prepared and studied. We have modified the dimer shape by variation of the connecting part between two bent-core units and changing the terminal chains (perfluoroalkyl, siloxanealkyl). Additionally, we have altered the inner bend angle value (120°, 60° and 148°) by utilization of different aromatic units. Mesomorphic properties of new dimers were established based on the texture observation in the polarizing microscope and DSC measurements. Moreover, x-ray structural analysis has been performed for selected dimers to confirm phase identification. For most of the studied dimers, nematic or columnar phases have been detected, for several compounds appearing in a nematic-columnar phase sequence on cooling from the isotropic phase. The studied dimers showed richer polymorphism than their monomeric counterparts.     

n‐Doping of Organic Electronic Materials Using Air‐Stable Organometallics: A Mechanistic Study of Reduction by Dimeric Sandwich Compounds

Several 19‐electron sandwich compounds are known to exist as “2×18‐electron” dimers. Recently it has been shown that, despite their air stability in the solid state, some of these dimers act as powerful reductants when co‐deposited from either the gas phase or from solution and that this behavior can be useful in n‐doping materials for organic electronics, including compounds with moderate electron affinities, such as 6,13‐bis[tri(isopropyl)silylethynyl]pentacene ( 3 ). This paper addresses the mechanisms by which the dimers of 1,2,3,4,5‐pentamethylrhodocene ( 1 b₂ ), (pentamethylcyclopentadienyl)(1,3,5‐trialkylbenzene)ruthenium (alkyl=Me, 2 a₂ ; alkyl=Et, 2 b₂ ), and (pentamethylcyclopentadienyl)(benzene)iron ( 2 c₂ ) react with 3 in solution. Vis/NIR and NMR spectroscopy, and X‐ray crystallography indicate that the products of these solution reactions are 3 ^.? salts of the monomeric sandwich cations. Vis/NIR kinetic studies for the Group 8 dimers are consistent with a mechanism whereby an endergonic electron transfer from the dimer to 3 is followed by rapid cleavage of the dimer cation. NMR crossover experiments with partially deuterated derivatives suggest that the C? C bond in the 1 b₂ dimer is much more readily broken than that in 2 a₂ ; consistent with this observation, Vis/NIR kinetic measurements suggest that the solution reduction of 3 by 1 b₂ can occur by both the mechanism established for the Group 8 species and by a mechanism in which an endergonic dissociation of the dimer is followed by rapid electron transfer from monomeric 1 b to 3 .     

Oligomeric liquid crystals: From monomers to trimers

A homologous series of linear liquid crystal trimers, the 4,4′-bis[ω-(4-methoxyazobenzene-4′-yloxy)alkoxy]azobenzenes, has been synthesized and characterized. The transitional properties of the trimers are compared with those of the corresponding series of dimers, the α,ω-bis(4-methoxyazobenzene-4′-oxy)alkanes, and monomers, the 4-methoxy-4′-alkoxyazobenzenes. Characteristically pronounced odd-even effects were seen for the transitional properties of both dimers and trimers on varying the spacer lengths. The clearing temperatures of the trimers were higher than those of the corresponding dimers, but as the length of the flexible spacers was increased this difference became rather small. The ratios of T _NI, and ΔS _NI/R for monomer:dimer and dimer:trimer are discussed. These are very similar to reported values for similar materials, suggesting that there may be a rather general relationship between the transitional properties of liquid crystal oligomers as the number of mesogenic units is increased.     

DIMER PHOTOPRODUCTS IN CYTIDYLYL-(3'-5') CYTIDINE

Abstract— When CpC is exposed to ultraviolet (u.v.) radiation, dimers are produced both photochemically and by dark reactions. A reaction scheme for the production of these dimers is presented. We have shown that a single dimer, CC₁, is initially produced photochemically. This is converted by a spontaneous reaction to a second dimer, CC₂. The dimer CC₂ may also spontaneously revert back to CC₁ and if no side reactions were involved a thermal equilibrium between these txo dimers would be established with about two to three times the concentration of CC₂, as of CC₁. The rate constants for the interconversion of these two dimers vary from about 0.05 to 0.4 hr^-1 over the pH range 2.7 to 8.4. The dimers of CpC have maximum stability near pH 7. The two dimers CC₁ and CC₂ can also be reversed to CpC by u.v. irradiation. Both these dimers in turn deaminate to dimers of UpC and then to UU. The rate constants for these deamination reactions are presented. These lie in the range 0.01 to 0.5 hr^-1 for the pH values studied. Possible structures for the two dimers are suggested.     

Twist bend nematic liquid crystals prepared by one-step condensation of 4-(4-Pentylcyclohexyl) benzoic acid and alkyl diol

Twist bend nematic (N_TB)-forming 9OCCHP5 and 11OCCHP5 dimers were synthesised by one-step condensation of 4-(4-pentylcyclohexyl) benzoic acid and alkyl diol with yields as high as 80%. Although each dimer formed the N_TB phase only during the cooling process in a narrow temperature width as large as 4°C, their equiweight mixture formed an N_TB phase during both the heating and cooling processes, displaying elliptical polygonal domains and rope-like optical texture. The N_TB temperature range became wider by 29–38°C and reduced the orientational order parameter significantly from 0.39 to 0.29 with decreasing temperature.     

Guest binding and new self-assembly of bisporphyrins

In organic medium, bisprophyrins 1-6 connected by aromatic linkers self-assemble via subtle forces such as van der Waals, pi-pi stacking, and CH/pi to form supramolecular dimers. The structures of bisporphyrin dimer 1.1 were discussed using our chemical shift simulation, revealing that 1.1 mainly adopts the self-complementary structure A. ESI mass experiments of the bisporphyrins showed that 1-4 form only the dimers; however, trimers as well as the dimers of 5 and 6 were observed in the gas phase. Thus, the assemblies of bisporphyrin 5 and 6 should adopt structure B, which still has a binding site to which another bisporphyrin can fit to form oligomeric structures. The dimerization constant of bisporphyrin 1 is dependent on the solvent polarity: the values decrease in the order of toluene > chloroform > 20% methanol-chloroform. The thermodynamic studies of the dimerization processes revealed that desolvation as well as pi-pi stacking interactions play a key role in the formation of the self-complementary dimers. The binding studies of bisporphyrin 1 with a variety of electron deficient aromatic guests 9-17 were carried out in chloroform. Soret and Q-bands of 1 showed the characteristic changes with the addition of guests 9-13 and 15, and large upfield shifts of their protons were observed in their complexation studies with (1)H NMR spectroscopy. These results suggested that the electron deficient aromatic guests bound within the cleft of bisporphyrin 1 via charge transfer as well as pi-pi stacking interactions between the guests and the porphyrin rings. The dimerization constant of 1.1 is much smaller than the association constant of 1.9, suggesting that the dissociation of dimer 1.1 can be regulated by binding of 9 within the cleft. The addition of 9 into the solution of 1.1 resulted in the quick dissociation of the dimer and the formation of 1.9.     

REMOVAL OF THYMINE-CONTAINING PYRIMIDINE DIMERS FROM UV LIGHT-IRRADIATED DNA BY S1 ENDONUCLEASE

Abstract— S₁ endonuclease was shown to remove thymine-containing pyrimidine dimers from UV-irradiated human DNA, although efficient removal could be demonstated only by using long digestion times, relatively high enzyme concentrations, and irradiation sufficient to yield dimer substitutions in DNA of 1 per 1W300 (dimers/base pair). Neutral and alkaline sucrose gradient analysis of strand break induction by S, of UV-irradiated DNA suggests that recognition of the dimer by S, is the limiting factor in its removal and dimer removal usually results from attack on the dimer containing DNA strand without the induction of a double-strand break.