Converting Nonliquid Crystals into Liquid Crystals by N-Methylation in the Central Linker of Triazine-Based Dendrimers.

Two triazine-based dendrimers were successfully prepared in 60-75% yields. These newly prepared dendrimers 2a and 2b containing the -NMe(CH2)2NMe- and the -NMe(CH2)4NMe- linkers between two G3 dendrons, respectively, exhibit columnar phases during the thermal process. However, the corresponding dendrimers 1a and 1b containing the -NH(CH2)2NH- and the -NH(CH2)4NH- linkers between two G3 dendrons, respectively, do not show any LC phases on thermal treatment. Computational investigations on molecular conformations reveal that N-methylation of the dendritic central linker leads dendrimers to possess more isomeric conformations and thus successfully converts non-LC dendrimers (1a and 1b) into LC dendrimers (2a and 2b).

An Unconventional Approach to Induce Liquid-Crystalline Phases of Triazine-Based Dendrons by Breaking Their Self-Assembly into Dimers.

Three triazine-based dendrons (1 a-c) were successfully prepared in 70-83 % yields. These newly prepared dendrons are found to be liquid crystalline (LC). Computational investigations on molecular conformations and dipoles of triazine-based dendrons reveal that the substituent on the central triazine unit interrupts strong dipole or H-bond interactions to avoid dimeric formation. The obtained dendrons, not favouring self-assembly into dimers but showing LC behaviours, provides evidence for an approach contrary to the conventional method of inducing LC behaviours of dendrons by dimer or trimer formation, mostly through H-bond interactions.

Bile acid-surfactant interactions at the liquid crystal/aqueous interface.

The interaction between bile acids and surfactants at interfaces plays an important role in fat digestion. In this paper, we study the competitive adsorption of cholic acid (CA) at the sodium dodecyl sulfate (SDS)-laden liquid crystal (LC)/aqueous interface formed with cyanobiphenyl (nCB, n = 5-8) and the mixture of 5CB with 4-(4-pentylcyclohexyl)benzonitrile (5PCH). We find that the critical concentration of CA required to displace SDS from the interface linearly decreases from 160 µM to 16 µM by reducing the alkyl chain length of nCB from n = 8 to n = 5 and from 16 µM to 1.5 µM by increasing the 5PCH concentration from 0 wt% to 19 wt% in the 5PCH-5CB binary mixture. Our results clearly demonstrate that the sensitivity of 5PCH-5CB mixtures for monitoring the interaction between CA and SDS at the LC/aqueous interface can be increased by one order of magnitude, compared to 5CB.

A small change in central linker has a profound effect in inducing columnar phases of triazine-based unconventional dendrimers.

Four unconventional triazine-based dendrimers have been prepared and characterized by (1) H and (13) C NMR spectroscopies, mass spectrometry, and elemental analysis. Based on DSC studies, polarizing microscopy, and powder XRD, two of these dendrimers, containing linkers with an odd number of carbon atoms, were observed to display columnar liquid-crystalline phases during thermal treatment. However, the other two dendritic analogues, containing linkers with an even number of carbon atoms, were not observed to behave correspondingly. Based on computer simulation, we reasonably assume that the dendrimers with an odd number of carbon atoms in their linkers distort their molecular shape and adopt two isomeric structures due to asymmetrical congestion. This reduces the molecular π-π face-to-face interaction, which in turn causes the dendrimers to form columnar LC phases during thermal treatment. However, the dendrimers with an even number of carbon atoms in their linkers have more symmetrical skeletons and do not display any liquid-crystalline phase upon thermal treatment. This new strategy should be applicable for eliciting the columnar liquid-crystalline properties of other types of unconventional dendrimers with rigid frameworks.

Preparation of unconventional dendrimers that contain rigid NH-triazine linkages and peripheral tert-butyl moieties for CO2 -selective adsorption.

Three unconventional dendrimers that contained rigid NH-triazine linkages and peripheral tert-butyl moieties were prepared by using a convergent approach and characterized by (1)H and (13)C NMR spectroscopy, mass spectrometry, and elemental analysis. Based on a thermogravimetric analysis study, these dendrimers were observed to display thermal stability at about 300 °C. The NH-triazine moiety, which possessed protonated and proton-free nitrogen sites (like the imidazole unit), displayed the capture of polarizable CO2 molecules through hydrogen-bond and/or dipole-quadrupole interactions. In addition, the adsorption of various amounts of CO2 and N2 at different pressures suggests that the dendritic pores, which arise from the stacking of the middle co-planar and rim protuberant dendrimers, Gn -N∼N-Gn (n=1-3), either swell or shrink at high pressure, thus indicating that these dendrimers may have a breathing ability.

Induction of the columnar phase of unconventional dendrimers by breaking the C2 symmetry of molecules.

Two triazine-based unconventional dendrimers were prepared and characterized by (1)H and (13)C NMR spectroscopy, mass spectrometry, and elemental analysis. Differential scanning calorimetry, polarizing microscopy, and powder XRD studies showed that these dendrimers display columnar liquid-crystalline phases during thermal treatment. This is ascribable to breaking of their C(2) symmetry. The molecular conformations of prepared dendrimers were obtained by computer simulation with the MM3 model of the CaChe program in the gas phase. The simulation showed that the conformations of the prepared dendrimers are rather flat and disfavor formation of the LC phase. However, due to C(2)-symmetry breaking, the prepared dendrimers have structural isomers in the solid state and thus show the desired columnar phases. This new strategy should be applicable to other types of unconventional dendrimers with rigid frameworks.

Formation of columnar liquid crystals on the basis of unconventional triazine-based dendrimers by the C3-symmetric approach.

Two series of unconventional triazine-based dendrimers with C(2) symmetry and C(3) symmetry were prepared. The newly prepared C(3)-symmetrical dendrimers were characterized by (1)H and (13)C NMR spectroscopy, mass spectrometry, and elemental analysis. Differential scanning calorimetry, polarizing microscopy, and powder XRD showed that the C(3)-symmetrical dendrimers display columnar liquid-crystalline phases during thermal treatment, but the C(2)-symmetrical dendrimers were not observed to behave correspondingly. The molecular conformations of C(3)- and C(2)-symmetrical dendrimers were obtained by computer simulation with the MM2 model of the CaChe program in the gas phase. The simulation results reasonably explain the different mesogenicities of C(3)- and C(2)-symmetric dendrimers. This new strategy should be applicable to other types of unconventional dendrimers with rigid frameworks for displaying columnar liquid-crystalline behavior.

Star-shaped mesogens of triazine-based dendrons and dendrimers as unconventional columnar liquid crystals.

Dendrons Gn-Cl and Gn-NH (n = 2-4) and novel dendrimers Gn-N approximately N-Gn (n = 2-4) based on triazine and piperazine units were efficiently prepared in good yields without employing the protection and deprotection processes and are fully characterized by 1H NMR and 13C NMR spectroscopies, elemental analysis, and mass spectroscopy. These compounds are transparent and possess good thermal stability. G4-Cl shows a monotropic columnar phase in a narrow range with a coexisting crystalline phase. Dendron G4-NH shows a rectangular column-phase, and dendrimer G4-N approximately N-G4 exhibits a monotropic hexagonal columnar phase. These identifications were supported by the polarizing optical scope and powder XRD studies.

Nanomaterials of triazine-based dendrons: convergent synthesis and their physical studies.

[structure: see text] Without employing protection and deprotection processes, two series of triazine-based dendrons were efficiently prepared by a convergent method and fully characterized; their physical properties, including acidic, thermal, electrical, and optical stabilities were also studied.