On the nematic-nematic phase transition in mixtures composed of sheet-shaped palladium organyls and apolar organic solvents

Abstract

The three sheet-shaped palladium organyls 1a-c exhibit lyotropic nematic properties in apolar organic solvents. The occurrence of two nematic lyomesophases was verified by the investigation of the orientational properties of these liquid crystalline systems. In cells with obliquely deposited SiO _x layers, the director of the high temperature phase N₂ is aligned in a homogeneous, planar manner. In the low temperature phase N₁, a different orientational pattern is observed. The specific pattern type depends on the deposition conditions of the SiO _x layers. In samples homeotropically aligned in the N₂ phase, the director is tilted away from the cell normal after the transition into the N₁ phase. These changes of orientation are reversible. The experimental observations presented here support our proposed model for the structural change at the nematic-nematic phase transition.     

On the nematic-nematic phase transition in mixtures composed of sheet-shaped palladium organyls and apolar organic solvents

The three sheet-shaped palladium organyls 1a-c exhibit lyotropic nematic properties in apolar organic solvents. The occurrence of two nematic lyomesophases was verified by the investigation of the orientational properties of these liquid crystalline systems. In cells with obliquely deposited SiO_x layers, the director of the high temperature phase N₂ is aligned in a homogeneous, planar manner. In the low temperature phase N₁, a different orientational pattern is observed. The specific pattern type depends on the deposition conditions of the SiO_x layers. In samples homeotropically aligned in the N₂ phase, the director is tilted away from the cell normal after the transition into the N₁ phase. These changes of orientation are reversible. The experimental observations presented here support our proposed model for the structural change at the nematic-nematic phase transition.     

Disc-shaped dinuclear palladium organyls Structure and phase behaviour of charge transfer induced mesophases [1]

Abstract

The recently synthesized non-calamitic/disc-shaped metal organyls containing two palladium atoms and eight flexible side chains represent the first case of metallo-mesogens exhibiting the nematic discotic (N_D) phase [2]. On doping with 2,4,7-trinitrofluorenone (TNF), a strong electron acceptor, the stabilization and/or induction of mesophases was observed. The phase behaviour of these binary systems and the structures of the mesophases displayed by them were studied by means of polarizing microscopy, differential scanning calorimetry, and X-ray scattering.     

Disc-shaped dinuclear palladium organyls Structure and phase behaviour of charge transfer induced mesophases [1]

The recently synthesized non-calamitic/disc-shaped metal organyls containing two palladium atoms and eight flexible side chains represent the first case of metallo-mesogens exhibiting the nematic discotic (N_D) phase [2]. On doping with 2,4,7-trinitrofluorenone (TNF), a strong electron acceptor, the stabilization and/or induction of mesophases was observed. The phase behaviour of these binary systems and the structures of the mesophases displayed by them were studied by means of polarizing microscopy, differential scanning calorimetry, and X-ray scattering.     

Monomeric, dimeric and hexameric resorcin[4]arene assemblies with alcohols in apolar solvents

Resorcin[4]arenes in an apolar solvent containing alcohols exist in three forms of self-assembled aggregates which have been characterised by the technique of diffusion NMR spectroscopy.     

Lyotropic liquid crystalline phase behaviour in amphiphile-protic ionic liquid systems

Approximate partial phase diagrams for nine amphiphile-protic ionic liquid (PIL) systems have been determined by synchrotron source small angle X-ray scattering, differential scanning calorimetry and cross polarised optical microscopy. The binary phase diagrams of some common cationic (hexadecyltrimethyl ammonium chloride, CTAC, and hexadecylpyridinium bromide, HDPB) and nonionic (polyoxyethylene (10) oleyl ether, Brij 97, and Pluronic block copolymer, P123) amphiphiles with the PILs, ethylammonium nitrate (EAN), ethanolammonium nitrate (EOAN) and diethanolammonium formate (DEOAF), have been studied. The phase diagrams were constructed for concentrations from 10 wt% to 80 wt% amphiphile, in the temperature range 25 °C to >100 °C. Lyotropic liquid crystalline phases (hexagonal, cubic and lamellar) were formed at high surfactant concentrations (typically >50 wt%), whereas at <40 wt%, only micelles or polydisperse crystals were present. With the exception of Brij 97, the thermal stability of the phases formed by these surfactants persisted to temperatures above 100 °C. The phase behaviour of amphiphile-PIL systems was interpreted by considering the PIL cohesive energy, liquid nanoscale order, polarity and ionicity. For comparison the phase behaviour of the four amphiphiles was also studied in water.     

Induction of nematic cholesteric (N*) phases by charge transfer complexation of disc-shaped multiynes [1]

Based on charge transfer interactions with the (chiral) electron acceptor (-)-2-(2,4,5,7-tetranitro-9-fluorenylidenaminooxy)propionic acid ((-)-TAPA), our easily accessible disc-shaped electron rich multiynes (for example, 1 and 2) give rise to two types of cholesteric nematic phases. Thus, the binary mixture of the nematic discotic (N_D) pentakis-(4-methylphenylethynyl)phenyl hexadecyl ether (2) with (-)-TAPA exhibits its twisted variant (N*_D). Likewise, but now in a ternary mixture, the homologue 1—peripherically unsubstituted and non-mesogenic—with the two electron acceptors (-)- TAPA and 2,4,7-trinitrofluorenone—both also non-liquid crystalline—shows cholesteric nematic properties, most probably however of a columnar type (N*_C). First results concerning these charge transfer induced cholesteric-nematic properties, including phase diagrams and the helical twist of the two systems presented here, are discussed on the basis of data obtained by polarizing microscopy and differential scanning calorimetry.     

Electrochemical transfer of [18F]fluoride from [18O]water into organic solvents ready for labeling reactions

For labeling reactions [¹⁸F]fluoride has to be separated from [¹⁸O]water and transferred into an organic solvent suitable for nucleophilic substitutions. An electrolytical method is described for depositing [¹⁸F]fluoride on a vitreous carbon electrode and releasing it directly into CH₃CN or DMSO. In the presence of Et₃N×3HF, [¹⁸F]fluoride is almost quantitatively released into acetonitrile. When using n.c.a conditions, i.e., Et₃N^.HCl, desorption of the ¹⁸F activity is almost 70% and 60% in acetonitrile and DMSO, respectively, already within 5 minutes.     

Solution behaviour of lead(II) carboxylates in organic solvents

The solution behaviour has been studied of a series of even chain length lead(II) carboxylates (octanoate to octadecanoate) and the odd chain length lead(II) heptadecanoate in a variety of non-complexing organic solvents and in alcohols. In agreement with previous studies, solubility increases dramatically above a certain temperature, which depends on solute concentration, chain length and solvent. This solution temperature is also affected by traces of water. These results are complemented by studies using vapour pressure osmometry, dynamic light scattering, ¹H and ¹³NMR spectroscopy. The results in water-free systems are consistent with the formation of rather ill-defined, polydisperse aggregates, which increase in size with concentration and decrease with temperature. These show similar local structure to lamellar mesophases in the pure lead(II) carboxylates, and are suggested to be formed by solvent induced swelling and break-up of these mesophases. In the presence of water, a more ordered structure is formed, in which a few water molecules are suggested to be bound to the lead(II) carboxylate headgroup.     

Lyotropic liquid crystalline phase behaviour of a monomeric and a polymeric monosaccharide amphiphile in aqueous solution

Monomeric and polymeric amphiphiles were synthesized which exhibit lyotropic liquid crystalline phases in aqueous solution. The hydrophobic group of the monomeric surfactant is a dodecane-group esterified with acrylic acid. The hydrophilic unit is a monosaccharide derivative. By radical polymerization the monomer (N-D(-)-gluco-N-methyl-(12-acryloyloxy)-dodecane-l-amide) is converted into the corresponding polymeric surfactant. The monomer as well as the polymer exhibit a lyotropic 1.c. phase of lamellar structure. Owing to the polymerization the regime of the lamellar phase is greatly enlarged for the polymer, compared to the monomeric sufactant. These results confirm earlier investigations on non-ionic ethylene-glycol surfactants.     

Aggregation of amphiphilic aminomethylated calix[4]resorcinarenes and the nonionic surfactant Triton-X-100 in organic solvents

Aggregation and intermolecular interactions of amphiphilic calix[4]resorcinarene (1), aminomethylated calix[4]resorcinarenes (AMC 2—7) with different structures of the upper rim (including the oxazine structure in 6 and 7) and hydrophobic substituents on the lower (2—5), upper (6), or both rims (7) in the absence and in the presence of the nonionic surfactant Triton-X-100 (8) and p-nitrophenol (9) in chloroform and 1,4-dioxane were studied by permittivity measurements and 2D ROESY ¹H NMR technique. The tendency of amphiphilic derivatives 1—7 toward self-aggregation and mixed aggregation with surfactant 8 primarily depends on the nature of both the solvent and the polar groups on the upper rim of calixarenes. In chloroform, AMC—8 aggregates show interactions of the methyl and methylene groups of the hydrophobic substituents of AMC with the ethyleneoxy fragments of surfactant 8, while in stable intermolecular complexes of 5 and 6 with compound 9, the methylene groups of the long-chain radicals of the AMC strongly interact with the aromatic protons ortho to the hydroxy group of 9. In 1,4-dioxane, calix[4]resorcinarenes 1 and 5 are bound in stable solvates, which prevents them from forming aggregates and mixed micelles.     

Lyotropic liquid crystal phase behaviour of the zwitterionic surfactants 4-n-tridecyl- and 4-n-heptadecyl-pyridinium N-oxide in water

The phase behaviour, liquid crystal structures and head group hydration of two 4-n-alkylpyridine-N-oxide surfactants have been studied using optical microscopy, DSC and ²H NMR spectroscopy. Only a limited swelling of the surfactant phase occurs in water, so that no micellar solution phase (L₁) occurs. The lamellar phase is the only mesophase observed. Water (²H) quadrupole splittings indicate that the head group binds c. 6 water molecules.     

Effect of composition of aqueous-organic solvents on polarographic behaviour of organic compounds

A review of the effect of the composition of aqueous-organic solvents on the polarographic behaviour of organic compounds is presented.     

Modular synthesis of unsymmetrical [1]benzothieno[3,2-b][1]benzothiophene molecular semiconductors for organic transistors

A modular approach to underexplored, unsymmetrical [1]benzothieno[3,2-b][1]benzothiophene (BTBT) scaffolds delivers a library of BTBT materials from readily available coupling partners by combining a transition-metal free Pummerer CH–CH-type cross-coupling and a Newman–Kwart reaction. This effective approach to unsymmetrical BTBT materials has allowed their properties to be studied. In particular, tuning the functional groups on the BTBT scaffold allows the solid-state assembly and molecular orbital energy levels to be modulated. Investigation of the charge transport properties of BTBT-containing small-molecule:polymer blends revealed the importance of molecular ordering during phase segregation and matching the highest occupied molecular orbital energy level with that of the semiconducting polymer binder, polyindacenodithiophene-benzothiadiazole (PIDTBT). The hole mobilities extracted from transistors fabricated using blends of PIDTBT with phenyl or methoxy functionalized unsymmetrical BTBTs were double those measured for devices fabricated using pristine PIDTBT. This study underscores the value of the synthetic methodology in providing a platform from which to study structure–property relationships in an underrepresented family of unsymmetrical BTBT molecular semiconductors.

A modular approach to underexplored, unsymmetrical [1]benzothieno[3,2-b][1]benzothiophene (BTBT) scaffolds, combining a transition-metal free Pummerer CH–CH-type cross-coupling and a Newman–Kwart reaction, delivers a library of BTBT materials.     

Calorimetric study on coordination of tridentate imidazolyl calix[6]arene ligands to zinc ion in organic solvents

Complexation of three kinds of tris(imidazolyl)calix[6]arenes containing alternate p-substituents (Calix-tBu, R(1) = R(2) = tert-butyl; Calix-NH(2), R(1) = tert-butyl, R(2) = NH(2); Calix-NO(2), R(1) = tert-butyl, R(2) = NO(2)) with Zn(ClO(4))(2)(H(2)O)(6) in acetonitrile, methanol, and THF was investigated via isothermal titration calorimetry (ITC). For the coordination of these calixarene ligands to Zn(II) in acetonitrile, typical one-phase exothermic titration curves were obtained, indicating the formation of 1:1 ligand-Zn(II) complexes accompanied by large conformational changes of the ligands. In contrast, the complexation in methanol was endothermic and dominated by favorable entropy changes. The entropy gains were achieved by extensive desolvation from both Zn(II) and the ligands. ITC measurements suggest a 2:1 ligand-Zn(II) complex formation in THF in the presence of excess ligands (Calix-NH(2) and Calix-NO(2)). The 2:1 complexes were converted to 1:1 complexes upon further addition of Zn(ClO(4))(2)(H(2)O)(6). The results indicate the important role of a coordinating solvent (acetonitrile) for direct formation of the 1:1 complexes under the conditions of excess ligand. Complexation of a ditopic ligand (Calix-Tri) with three triazole moieties on the wider rim was also studied via ITC. The first coordination of the imidazole moieties to Zn(II) was an exothermic process. This was followed by the entropically favorable coordination of the triazole moieties to the divalent cation. We have also investigated exchange of the fourth ligand (H(2)O) of the Zn(II) complex of Calix-NH(2) with butylamine, heptylamine, acetonitrile, and acetamide in a noncompetitive solvent, THF. The ΔH(0) tended to decrease upon increasing the electron-pair-donating ability of the guest ligand, whereas it was also affected by an entropic term due to restricted rotation of the guest ligand inside the calixarene cavity.     

Substitution pattern and stereochemistry versus liquid crystalline behaviour [1]

Abstract

Selectively O-alkylated inositols of myo-, scyllo- and chiro-configuration allow detailed studies of the relationship between the substitution pattern in the cyclohexane ring and the liquid crystalline properties observed to be made for these mainly novel cyclic compounds containing hydroxyl functions. The types of thermotropic mesophase formed and containing hydrogen bonds are strongly influenced by the number and the stereochemical arrangement of both the hydroxyl groups and the alkyloxy chains, as well as by their positions on the cyclohexane ring.

The mesophases of the various new inositol ethers have been studied by polarizing optical microscopy and differential scanning calorimetry, and are discussed here in comparison with known systems, as a function of the above mentioned structural factors.     

Contribution enthalpic in the interaction of activated carbon with polar and apolar solvents

A method is presented for calculating the contribution that enthalpies make for every component of mixtures of activated carbon–water and activated carbon–hexane to the immersion enthalpy using the concepts that are used in the solution enthalpies. The immersion enthalpies of microporous activated carbon in water and in hexane have values from ?18.97 to ?27.21 and ?25.23 to ?47.89 J g^?1, respectively. From the immersion enthalpies and mass relation of the activated carbon in each of the solvents, the differential enthalpies are calculated for the activated carbon in water, Hw_DIFac, with values between ?15.95 and ?26.81 J g^?1, as are the differential enthalpies for the activated carbon in hexane, ΔHh_DIFac, with values between ?6.86 and ?46.97 J g^?1. For a low mass relation of the mixture components the contributions to the immersion enthalpy of the activated carbon and water differ by 3.20 J g^?1, while the difference between the contributions of the activated carbon and hexane is 19.41 J g^?1.     

Anion exchange behaviour of various metal ions in sulphuric acid solutions containing organic solvents

Summary The anion-exchange behaviour of 10 di- and tervalent metal ions in sulphuric acid solutions containing high percentages of water-miscible organic solvents is described. The studies were carried out using the strongly basic anion-exchange resin Dowex 1 (sulphate form) and the solvents methanol, ethanol, n-propanol, isopropanol, acetone, methyl glycol, and tetrahydrofuran. The results of these experiments reveal that at a constant acidity the batch-distribution co-efficients of all metal ions, as a rule, increase with an increase in the percentage of the organic component.

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Zusammenfassung Das Anionenaustauschverhalten von 10 zwei- und dreiwertigen Metallionen in schwefelsauren Lösungen, die hohe Konzentrationen an mit Wasser mischbaren organischen Lösungsmitteln enthalten, wird beschrieben. Die Untersuchungen wurden am stark basischen Anionenaustauscher Dowex 1 (Sulfatform) unter Anwendung der Lösungsmittel Methanol, Äthanol, n-Propanol, Isopropanol, Aceton, Methylglykol und Tetrahydrofuran ausgeführt. Aus den Ergebnissen der Versuche geht hervor, daß bei konstanter Acidität die Verteilungskoeffizienten aller Metallionen in der Regel mit Zunahme des Prozentgehaltes der organischen Komponente ansteigen.