Structure and mesomorphism of neodymium(III) alkanoates

The structural and thermal behavior of all members of the homologous series of neodymium(III) alkanoates, ranging from neodymium(III) butyrate to neodymium(III) eicosanoate are described. Neodymium(III) butyrate monohydrate, Nd(C3H7COO)3.H2O crystallizes in space group P1 (No. 2), Z = 2. The lattice parameters are a = 9.824(2) A, b = 11.974(2) A, c = 14.633(2) A, alpha = 86.21(2) degrees, beta = 75.92(2) degrees, gamma = 77.97(2) degrees. The crystal structure consists of ionic layers of neodymium ions, separated by bilayers of butyrate anions. In the ionic layers, the neodymium ions are connected by bridging tridentate carboxylate groups to zigzag chains, whereas the chains are connected among themselves by bridging bidentate carboxylate groups. The two crystallographically different neodymium ions are both having coordination number 9, with a geometry close to a monocapped square antiprism. The structure of the higher homologues can be derived from the structure of neodymium butyrate by extending the alkyl chains. These compounds have a lamellar bilayer structure with planes of neodymium(III) ions coordinated to the carboxylate groups and with the alkyl chains in an all-trans conformation. All homologous compounds from neodymium(III) pentanoate to neodymium(III) pentadecanoate display a thermotropic mesophase, which was identified by high-temperature X-ray diffraction as a smectic A phase. For the series from neodymium(III) pentanoate to neodymium(III) undecanoate an additional high viscosity mesophase is present between the crystalline state and the smectic A mesophase.     

Thermal behaviour of lanthanum(III) alkanoates

The mesophase behaviour of the lanthanum(III) alkanoates [La(C_xH_2x+1COO)₃] (x =3-19) has been investigated by hot-stage polarizing optical microscopy, differential scanning calorimetry and high-temperature X-ray diffraction. Lanthanum(III) butyrate monohydrate shows no mesomorphism, whereas for the remaining short chain homologues (x = 4-9) a highly viscous mesophase M and a smectic A phase were observed. The longer chain lanthanum(III) soaps (x = 10-19) exhibit only a smectic A phase. However, the chain length has a pronounced effect on the transition temperatures. The thermal behaviour of lanthanum(III) alkanoates is compared with that of other lanthanide(III) alkanoates.     

Thermal behaviour of lanthanum(III) alkanoates

The mesophase behaviour of the lanthanum(III) alkanoates [La(C_xH_2x+1COO)₃] (x =3-19) has been investigated by hot-stage polarizing optical microscopy, differential scanning calorimetry and high-temperature X-ray diffraction. Lanthanum(III) butyrate monohydrate shows no mesomorphism, whereas for the remaining short chain homologues (x = 4-9) a highly viscous mesophase M and a smectic A phase were observed. The longer chain lanthanum(III) soaps (x = 10-19) exhibit only a smectic A phase. However, the chain length has a pronounced effect on the transition temperatures. The thermal behaviour of lanthanum(III) alkanoates is compared with that of other lanthanide(III) alkanoates.     

Mesomorphic properties of symmetrical and asymmetrical triphenylene homologues possessing fluoroalkylated side chains

Two types of homologues (symmetrical and asymmetrical in rotational symmetry) of novel triphenylene compounds possessing fluoroalkyl and alkyl side chains were synthesized via an alternative method. X-ray diffraction and DSC measurements showed that these homologues are thermotropic liquid crystals with a hexagonal columnar (Col_h) mesophase. The phase transition temperatures (Col_h-Iso) for both symmetrical and asymmetrical fluoroalkyloxytriphenylenes increase to about 180°C, and are independent of fluoromethylene chain and the rotational symmetry of chemical structure. The Col_h phase of symmetrical and asymmetrical fluoroalkyloxytriphenylenes possessing three fluoroalkyl side chains are more stable than fluoroalkyloxytriphenylenes possessing six fluoroalkyl side chains and alkyloxytriphenylenes. The X-ray diffraction patterns for symmetrical and asymmetrical fluoroalkyloxytriphenylenes, fluoroalkyloxytriphenylenes and alkyloxytriphenylenes in the wide-angle region are compared.     

Structural study of crystalline and columnar copper (II) soaps

A homologous series of binuclear copper (II) linear chain alkanoates together with two branched chain and one aromatic substituted copper (II) alkanoates have been synthesized and studied by polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction. All of these are crystalline at room temperature, they are mesomorphic in nature above c. 100°C, with the exception of copper propionate which remains crystalline up to its thermal decomposition above 200°C. A systematic study has shown that the linear chain alkanoates, starting from the pentanoic derivative, produce columnar mesophases with hexagonal symmetry. Columns of polar copper carboxylate groups are surrounded by disordered aliphatic chains, and form a two dimensional hexagonal lattice. The repeat unit in a column is a binuclear dicopper tetracarboxylate complex. Two transition regimes have been detected leading from the crystal to the columnar mesophase: one dominated by the interactions between the polar heads, the other by the interactions between aliphatic chains. In the special case of the butyric derivative, the columnar mesophase obtained is rectangular in symmetry. Instead of being oriented perpendicular to the columnar axis and superposed in a four fold helicoidal fashion, the repeat units in the columns are tilted and all shifted in the same direction with respect to one another.     

Crystal Structures and Thermal Behaviour of Lanthanide(III) Hexanoate 1, 10‐Phenanthroline Complexes, [M(C5H11CO2)3(phen)] and [Tm(C5H11CO2)2(NO3)(phen)]

Lanthanide(III) hexanoate 1, 10‐phenanthroline complexes crystallise in the space group P2₁/n. The compounds consist of dimers, whereby two lanthanide ions are held together by two bidentate bridging and two tridentate bridging carboxylate groups. The first coordination sphere of the lanthanide ions is completed by one bidentate chelating carboxylate group and by one bidentate 1, 10‐phenanthroline molecule, resulting in the coordination number 9. The dimers have a spherical form, which has important consequences for the thermal properties of complexes. The basic idea behind the preparation of this type of compounds is the stabilisation of the ionic lanthanide layer, so that the smaller lanthanide ions (from which the normal alkanoates do not show mesomorphism because they are too small) show liquid crystallinity. The stabilisation of the ionic layer was successful, expressed by the high melting temperatures, but mesomorphism is not observed. The absence of mesomorphism is related to the isotropic structure of the compounds. A lower symmetry is obtained when a hexanoate group is replaced by a nitrate group. Thulium(III) dihexanoate nitrate 1, 10‐phenanthroline crystallises in the space group P1¯. However, this compound also shows a spherical dimeric structure, but no mesomorphism.     

Synthesis and Mesophase Behavior of Phenylthiophene Based Amphiphilic Molecules

Novel amphiphilic molecules consisting of a rigid 2‐phenylthiophene core, with a polar flexible tri(oxylethylene) moiety attached to the phenyl ring and one or two alkyl chains attached to the thiophene ring at the other side have been synthesized by using Ni(II) and Pd(0) catalyzed coupling reaction as key steps. The tri(oxylethylene) moieties were terminated with hydroxyl group, sodium carboxylate group and lithium carboxylate group respectively. The thermotropic and solvent induced liquid crystalline behavior of these substances was investigated by polarized optical microscopy, differential scanning calorimetry and X‐ray diffraction. Thereby the influence of the terminal groups attached to the tri(oxylethylene) moities as well as the influence of the length and the number of the alkyl chains on the mesophase behavior were investigated. The single alkyl chain Na‐carboxylate termianted derivatives show smectic A phases, double alkyl chain Na‐carboxylate terminated derivatives show a thermo tropic hexagonal columnar mesophase, while columnar mesophases are found in both single and double alkyl chain Li‐carbonate terminated derivatives. The model for molecular organization in the hexagonal columnar mesophase is established.     

The mesomorphic behaviour of cyanopropylalkyldimethylammonium bromides

A homologous series of N-cyanopropyl-N-alkyl-N,N-dimethylammonium bromides was synthesized and characterized. Its thermotropic liquid crystalline behaviour was studied by differential scanning calorimetry, polarizing optical microscopy, dilatometry, and X-ray diffraction. A smectic A mesophase was thus identified. The smectic layers were found to be formed of two ionic planes alternately separated by sub-layers of disordered alkyl chains and cyanopropyl groups. The smectic structure was compared with that of the crystal at room temperature and also that of the smectic T structure of the N,N-dialkyl-N,N-dimethylammonium bromides already described in the literature.     

Synthesis and thermal behaviour of liquid crystalline pyridinium bromides containing a biphenyl core

A range of new pyridinium bromides was synthesized by the quaternization of different substituted pyridines with a group containing a biphenyl core and alkyl chains of differing lengths. The phase behaviour of the pyridinium bromides was studied by differential scanning calorimetry, polarizing optical microscopy and powder X-ray diffraction. It is shown that pyridinium moieties, linked to a rod-like biphenyl core via an alkyl spacer, can form ionic liquid crystals. Unsubstituted pyridinium groups promote mesomorphism. Liquid crystalline phases are formed only from 2- and 4-ethyl substituted pyridinium groups with sufficiently long alkyl terminal chains and spacers; i.e. decyl chains on both sides of the biphenyl core. Both the substitution pattern at the pyridinium group and the alkyl chain length have an influence on the polymorphism of the smectic phases. 3,5-Dimethyl substitution hinders mesophase formation.     

Synthesis and thermal behaviour of liquid crystalline pyridinium bromides containing a biphenyl core

A range of new pyridinium bromides was synthesized by the quaternization of different substituted pyridines with a group containing a biphenyl core and alkyl chains of differing lengths. The phase behaviour of the pyridinium bromides was studied by differential scanning calorimetry, polarizing optical microscopy and powder X-ray diffraction. It is shown that pyridinium moieties, linked to a rod-like biphenyl core via an alkyl spacer, can form ionic liquid crystals. Unsubstituted pyridinium groups promote mesomorphism. Liquid crystalline phases are formed only from 2- and 4-ethyl substituted pyridinium groups with sufficiently long alkyl terminal chains and spacers; i.e. decyl chains on both sides of the biphenyl core. Both the substitution pattern at the pyridinium group and the alkyl chain length have an influence on the polymorphism of the smectic phases. 3,5-Dimethyl substitution hinders mesophase formation.     

Ionic liquid crystals based on viologen dimers: tuning the mesomorphism by varying the conformational freedom of the ionic layer

We investigated the liquid crystal behaviour of newly synthesised bistriflimide salts of symmetric viologen dimers. A smectic A phase was observed for intermediate spacer lengths and for relatively long lateral alkyl chains. The systems were characterised by thermal analysis, polarised optical microscopy, X-ray scattering and solid-state NMR. An intermediate ordered smectic phase was also exhibited by the compounds (except for systems with very short lateral chains) consisting of molten layers of alkyl chains and partially ordered ionic layers. These results, relating to the mesomorphic behaviour of viologen salts, are qualitatively compared to those of the more common imidazolium salts, highlighting the importance of the conformational degrees of freedom of the anions and of the cationic core. It appears that fine tuning of the conformational degrees of freedom of the ionic layer is an important component of mesophase stabilisation.     

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.     

Coordination Chemistry of Lanthanides at “High” pH: Synthesis and Structure of the Pentadecanuclear Complex of Europium(III) with Tyrosine

A five-coordinate chloride ion is believed to template the assembly of a pentadecanuclear lanthanide complex of europium(III ). This cluster (see picture) has been prepared by coordination of europium(III ) perchlorate with tyrosine at about pH 6. Single crystal X-ray analysis established an unprecedented structure in which 15 constituent europium(III ) ions are organized into three parallel pentagonal layers.     

The mesomorphic behaviour of cyanopropylalkyldimethylammonium bromides

Abstract

A homologous series of N-cyanopropyl-N-alkyl-N,N-dimethylammonium bromides was synthesized and characterized. Its thermotropic liquid crystalline behaviour was studied by differential scanning calorimetry, polarizing optical microscopy, dilatometry, and X-ray diffraction. A smectic A mesophase was thus identified. The smectic layers were found to be formed of two ionic planes alternately separated by sub-layers of disordered alkyl chains and cyanopropyl groups. The smectic structure was compared with that of the crystal at room temperature and also that of the smectic T structure of the N,N-dialkyl-N,N-dimethylammonium bromides already described in the literature.     

Investigation of the Structures of the Crystalline and Columnar Phases of Linear Chain Copper(II) Alkanoates

Binuclear copper(11) complexes of fatty acids crystallize at room temperature in a lamellar lattice that has been characterized by X-ray diffraction. A transition to a thermotropic columnar mesophase is observed at about 110-120°C for each compound of the series n = 12 to n = 22, n being even and equal to the number of carbon atoms in the corresponding fatty acid. This columnar mesophase has been investigated by polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction. Columns of polar copper carboxylate groups are surrounded by disordered aliphatic chains, and form a two-dimensional hexagonal lattice. The repeating unit in a column is a binuclear dicopper tetracarboxylate complex.     

Liquid crystal phases generated by supramolecular self-assembly of biforked amphiphilic imidazoles

Functional groups with the capability of hydrogen bonding are widely used in the molecular design and preparation of liquid crystalline supramolecular systems, a rapidly growing area of materials showing a high sensitivity towards external stimuli. A series of novel imidazole-containing Schiff's bases replenishing the family of supramolecular liquid crystals has been synthesised and characterised by proton nuclear magnetic resonance, Fourier transform infrared, and ultraviolet–visible spectroscopy, and elemental analyses. Variation of lengths of the terminal alkyl substituents in the obtained amphiphilic imidazoles within 6, 8, 10, 12, 14 and 16 carbon atoms leads to significant changes in their thermal behaviour, micro-segregation and supramolecular self-assembly. Lower homologues were non-mesomorphic, while intermediate members of the homologous series exhibited monotropic bilayered smectic and columnar mesophases. A higher homologue with 16 carbon atoms has an increased trend towards crystallisation of the aliphatic chains and did not exhibit mesomorphism again. The liquid crystalline mesophases were identified and investigated by polarised optical microscopy, differential scanning calorimetry, X-ray diffraction and thermal emission microscopy methods. According to X-ray diffraction characteristics, the smectic mesophase has a bilayered structure where the hydrophilic imidazole groups form a continuous hydrogen bonded network. The interface curvature created by the second alkyl chain leads to the appearance of columnar nanostructures in homologues with 12 and 14 aliphatic carbon atoms.     

Designer ionic liquid crystals based on congruently shaped guanidinium sulfonates

Ionic liquid crystals are mesogenic compounds that consist of cations and anions, usually rod-like cations and spherical anions. Herein we report a new method for the synthesis of ionic liquid crystals by using cations and anions of the same molecular shape with oppositely charged head groups. Thus, 4-alkoxyphenylpentamethylguanidinium 4-alkoxyphenylsulfonate ion pairs have been synthesised. 4-Alkoxyphenylpentamethylguanidinium iodides were also prepared to determine the influence of congruently shaped anions, in comparison with their spherical counterparts, on mesophase behaviour, which was investigated by differential scanning calorimetry (DSC), polarising optical microscopy (POM) and X-ray diffraction (XRD). All the liquid crystalline salts exhibit smectic A mesophases with strongly interdigitated bilayer structures. The guanidinium sulfonate ion pairs show mesomorphic properties from shorter alkyl chain lengths (≥C(9)) and lower melting points (≈10 K), whereas the corresponding guanidinium iodides are liquid crystalline for longer alkyl chain lengths (≥C(14)). For chains with ≥C(18), however, the mesophase range decreases for the sulfonate ion pairs, but not for the iodide salts.     

Mixed copper-lanthanide metallomesogens

This paper describes the first examples of heteropolynuclear metallomesogens that contain both a transition metal ion and a trivalent lanthanide ion. Adducts were formed between a mesomorphic [Cu(salen)] complex (salen=2,2'-N,N'-bis(salicylidene)ethylenediamine) with six terminal tetradecyloxy chains and a lanthanide nitrate (Ln=La, Gd). Different stoichiometries were found, depending on the lanthanide ion: a trinuclear copper-lanthanum-copper complex [La(NO(3))(3)(Cu(salen))(2)] and a binuclear copper-gadolinium complex [Gd(NO(3))(3)Cu(salen)]. The compounds exhibit a hexagonal columnar mesophase (Col(H)) over a wide temperature-range with rather low melting temperatures. Although the clearing point could be observed for the parent [Cu(salen)] complex, the mixed f-d complexes decomposed in the high-temperature part of the mesomorphic domain before clearing. On the basis of X-ray diffraction measurements and molecular modelling, a structural model for the mesophase of the metal complexes is proposed.     

The SmCPA phase in five‐ring bent‐core compounds derived from 5‐methoxyisophthalic acid

The synthesis and mesophase characterization of a homologous series of five‐ring bent‐core compounds derived from 5‐methoxyisophthalic acid are described. Most of the compounds exhibit a polar antiferroelectric smectic C phase. Replacement of the terminal n‐alkoxy chains by n‐alkyl carboxylate groups, not only destabilizes the formation of mesophases but induces a calamitic mesophase. However, extension of the arms of the bent‐core molecule by a phenyl moiety stabilizes the switchable phase. The mesophases were investigated using a combination of polarizing optical microscopy, differential scanning calorimetry, X‐ray diffraction and electro‐optical methods.     

Sulfur makes the difference: synthesis and mesomorphic properties of novel thioether-functionalized imidazolium ionic liquid crystals

Novel thioether-linked imidazolium ionic liquid crystals were synthesized starting from methyl 2-mercaptoacetate. The mesomorphic properties were determined by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X-ray diffraction. All mesogens displayed smectic A mesophase geometries with strongly interdigitated bilayer structures. Comparison of the thioether-linked imidazolium salts with the corresponding amine- and amide-linked imidazolium salts as well as simple N-alkyl-imidazolium salts showed that both mesophase width and stability increased with increasing softness of the linking unit, thus indicating the beneficial effect of sulfur. Additionally, an increase of the length of the linking unit decreased the interdigitation of the alkyl chains.