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.     

Trimetallic Nickel–Lanthanum and Nickel–Gadolinium Metallomesogens

Adducts were formed between a mesomorphic Ni(salen) complex [salen=2,2′-N,N′-bis(salicylidene)ethylenediamine] with six terminal alkoxy chains and a lanthanide nitrate (Ln=La, Gd). Different alkoxy chain lengths were used: OC¹²H²⁵, OC¹⁴H²⁹, OC¹⁶H³³ and OC¹⁸H³⁷. Trinuclear nickel–lanthanum and nickel–gadolinium complexes [Ln(NO³)³{Ni(salen)}²] were obtained. The compounds exhibit a wide-temperature-range hexagonal columnar mesophase (Col^H) with rather low melting points. The mesophase stability ranges of both the parent nickel complexes and the nickel–lanthanide complexes decrease with increasing chain length. A decrease in the mesophase stability range over the lanthanide series was also observed. The results are compared with those of similar copper–lanthanide complexes. A marked difference is the higher thermal stability of the nickel–lanthanide complexes in comparison with the copper–lanthanide complexes.     

Columnar metallomesogens derived from unsymmetrical pyrazoles

The synthesis and mesomorphism for two series of unsymmetrical pyrazoles and their nickel(II) complexes were described. This is the first example of nickel complexes exhibiting columnar phase. The derivatives with two alkoxy chains exhibited smectic A or smectic C phases; however, all derivatives with four alkoxy chains formed hexagonal columnar phases. In contrast, all nickel(II) complexes 1a formed hexagonal columnar phases. The crystal and molecular structures of 1-(4-propyloxyphenyl)-2-(3-(4-propyloxyphenyl)-1H-pyrazol-5-yl)ethanone were determined, and it crystallizes in the triclinic space group P-1. The overall molecular shape is considered as rod-shaped. The pyrazole and one phenyl ring were coplanar, however, they were not coplanar with other phenyl ring by a dihedral angle of ca. 66.2°. A dimeric structure formed by an intermolecular H-bond (2.11 Å) and a weak π-π interaction (3.51 Å) was observed, which was probably attributed to the formation of the mesophase. The XRD experiments confirmed their structures of the mesophases.     

Thermotropic liquid crystals based on chito-oligosaccharides. II. Discotic columnar liquid crystals in chitobiose octaalkanoates and chitotriose hendecaalkanoates

Chitobiose octaalkanoates and chitotriose hendecaalkanoates with varying acyl pendant lengths were synthesized and their mesophase properties studied. Both series of derivatives showed an enantiotropic mesophase in a wide temperature region below 200°C. An X-ray diffraction analysis revealed the mesophase to be of a hexagonal columnar type, in which the columns built up by a periodic stacking of chitobiose or chitotriose cores are packed into a two dimensional hexagonal lattice. The mesophase is thus similar to the hexagonal ordered columnar (D_ho) phase in discotics. Compared with cello-oligosaccharide counterparts, the diameter of the column is fairly large and the stacking period somewhat short; these can be interpreted as resulting from the intermolecular hydrogen bonding which is formed between the secondary amide group in the C2 position and the ester group.     

Self‐Assembly in Helical Columnar Mesophases and Luminescence of Chiral 1H‐Pyrazoles

Chiral polycatenar 1H‐pyrazoles self‐assemble to form columnar mesophases that are stable at room temperature. X‐ray diffraction and CD studies in the mesophase indicate a supramolecular helical organization consisting of stacked H‐bonded dimers. The liquid‐crystalline compounds reported are 3,5‐bis(dialkoxyphenyl)‐1H‐pyrazoles that incorporate two or four dihydrocitronellyl chiral tails. It can be observed that the grafting of these branched chiral substituents onto the 3,5‐diphenyl‐1H‐pyrazole core has a beneficial role in inducing mesomorphism, because isomeric linear‐chain compounds are not liquid crystalline; this is not the usual scheme of behavior. Furthermore, the molecular chirality is transferred to the columnar mesophase, because preferential helical arrangements are observed. Films of the compounds are luminescent at room temperature and constitute an example of the self‐organization of nondiscoid units into columnar liquid‐crystalline assemblies in which the functional molecular unit transfers its properties to a hierarchically built superstructure.     

Mesomorphic flexible chain polymers based on silicon

Poly(dialkylsiloxane)s and poly(dialkylsilane)s form a similar type of columnar mesophase. Although, the polysilanes are stiffer than polysiloxanes, both classes of polymers may be considered to be flexible due to the ability to form chain-folded crystals. Chain flexibility rather than the presence of chain stiffness determines whether the columnar mesophase is formed. A certain amphiphilic character does not appear to be required, as polysiloxanes with short side groups, e.g. polydiethylsiloxane display the same mesophase behaviour as polydialkylsilanes with long side chains and other nonpolar flexible chain molecules. The importance of the entropy gain upon conformational disordering is reflected in the increase in temperature stability with increasing alkyl side group length and the absence of mesophase behaviour in the case of the dimethyl substituted polymers     

Tunable Emissive Lanthanidomesogen Derived from a Room‐Temperature Liquid‐Crystalline Schiff‐Base Ligand

A novel photoluminescent room‐temperature liquid‐crystalline salicylaldimine Schiff base with a short alkoxy substituent and a series of lanthanide(III) complexes of the type [Ln(LH)₃(NO₃)₃] (Ln=La, Pr, Sm, Gd, Tb, Dy; LH=(E)‐5‐(hexyloxy)‐2‐ [{2‐(2‐hydroxyethylamino)ethylimino]methyl}phenol) have been synthesized and characterized by FTIR, ¹H and ¹³C NMR, UV/Vis, and FAB‐MS analyses. The ligand coordinates to the metal ions in its zwitterionic form. The thermal behavior of the compounds was investigated by polarizing optical microscopy (POM) and differential scanning calorimetry (DSC). The ligand exhibits an enantiotropic hexagonal columnar (Col_h) mesophase at room temperature and the complexes show an enantiotropic lamellar columnar (Col_L) phase at around 120 °C with high thermal stability. Based on XRD results, different space‐filling models have been proposed for the ligand and complexes to account for the columnar mesomorphism. The ligand exhibits intense blue emission both in solution and in the condensed state. The most intense emissions were observed for the samarium and terbium complexes, with the samarium complex glowing with a bright‐orange light (ca. 560–644 nm) and the terbium complex emitting green light (ca. 490–622 nm) upon UV irradiation. DFT calculations performed by using the DMol3 program at the BLYP/DNP level of theory revealed a nine‐coordinate structure for the lanthanide complexes.     

Mesomorphic properties of copolyesters of 3,6-linked triphenylene-based units and polymethylene spacers

Main chain discotic liquid crystalline polymers consisting of triphenylene-based units and alkyl spacers (C8, C10 and C12), connected by ester linkages in the 3- and 6-positions of triphenylene, have been synthesized and their mesomorphic properties were studied by DSC, polarizing optical microscopy and X-ray diffraction. It was found that these polymers exhibit a hexagonal columnar (Col h ) mesophase with intracolumnar order over a wide temperature range. The clearing temperature decreases on increasing the spacer length. It was found that the clearing temperatures are rather higher than that of the corresponding triphenylene monomer having six hexyloxy chains. These polymers form an ordered columnar mesophase, while the corresponding monomeric mesogen shows a disordered columnar phase. In the polymeric system, the fluctuations of the disc-like units in the mesophase are restricted by the connection of the mesogenic units, which stabilizes the columnar mesophase.     

Synthesis and characterization of liquid crystalline monofunctionalized 'two chain' diols and corresponding low molecular weight siloxane derivatives

The selective synthesis and the thermal behaviour of some cis, cis-(3,5-dihydroxycyclohexyl) 3,4-(alkenyloxy, alkyloxy)benzoates (monofunctionalized 'two chain' diols) are described. Thus, several 3-(alkyloxy)-4-(undecenyloxy)benzoic acids and 4-(decyloxy)-3-(undecenyloxy)benzoic acid have been obtained. The monofunctionalized 'two chain' diols form a hexagonal columnar mesophase through hydrogen bonding. Subsequently, low molecular weight liquid crystalline siloxanes, model compounds for polymers, i.e. two twins and one cyclic product, were synthesized via a hydrosilylation reaction. With respect to the 'two chain' diols, the observed hexagonal columnar mesophase was stabilized and the intercolumnar distance was extended by the siloxane moieties. Remarkably, the thermal behaviour of the cyclosiloxane differs from that of the twins. A cubic mesophase, which can be observed very rarely in thermotropic mesogens, was formed at temperatures below the hexagonal columnar phase.     

Photoluminescent nickel(II)-metallomesogens derived from salphen ligands: influence of halogens at the spacer on mesomorphism and emission properties

Three new series of photoluminescent nickel(II) metallomesogens, [NiL]; H₂L = N,N′-Bis(4-n-alkoxysalicylidene)-4-fluoro/bromo/chloro-1,2-diaminobenzene (n = 12, 14, 16) based on ‘salphen’ ligands have been synthesised and their mesomorphic and photophysical properties explored. The complexes, isolated as orange microcrystalline solids were characterised by elemental analyses, FT-IR, ¹H NMR and UV-visible spectroscopy. Thermal studies show all the compounds to be enantiotropic liquid crystals displaying columnar mesophase over a wide temperature range. Electronegativity and steric requirement of the halogen substituent at the ligand’s spacer remarkably influence the 2-D packing of the columns in the lattice in these complexes controlling the supramolecular mesomorphic order and photoluminescence. The mesophase behaviour of the fluoro-substituted complex is characterised by a transition from a columnar oblique (p1) to columnar rectangular (p2mm) phase, former stable till ambient temperature. The chloro and bromo analogues, on the other hand, displayed exclusively columnar rectangular (p2mm) mesophase with the former transforming into a glassy state and latter into a crystalline phase during cooling to ambient temperature. Molecular model based on interdigitated anti-parallel and back to back arrangements in the different columnar mesophase are proposed on the basis of X-ray diffraction (XRD) studies. The complexes emit in the blue region when excited with near UV wavelength.     

Mesomorphic properties of copolyesters of 3,6-linked triphenylene-based units and polymethylene spacers

Main chain discotic liquid crystalline polymers consisting of triphenylene-based units and alkyl spacers (C8, C10 and C12), connected by ester linkages in the 3- and 6-positions of triphenylene, have been synthesized and their mesomorphic properties were studied by DSC, polarizing optical microscopy and X-ray diffraction. It was found that these polymers exhibit a hexagonal columnar (Col_h) mesophase with intracolumnar order over a wide temperature range. The clearing temperature decreases on increasing the spacer length. It was found that the clearing temperatures are rather higher than that of the corresponding triphenylene monomer having six hexyloxy chains. These polymers form an ordered columnar mesophase, while the corresponding monomeric mesogen shows a disordered columnar phase. In the polymeric system, the fluctuations of the disc-like units in the mesophase are restricted by the connection of the mesogenic units, which stabilizes the columnar mesophase.     

Discotic liquid-crystalline materials based on porphycenes: a mesogenic metalloporphycene-tetracyanoquinodimethane (TCNQ) adduct

A number of substituted zinc(II) porphycenes and porphyrins have been synthesized as potentially mesogenic materials. One of the resulting porphycenes, bearing eight decyloxy chains, exhibits two mesophases, a transient lamellar phase (Lam) and a highly ordered lamello-columnar phase (L(Col)), with remarkably different structural characteristics. The same zinc(II) porphycene also forms an electron donor-acceptor (EDA) complex with tetracyanoquinodimethane (TCNQ), generating a hexagonal columnar mesophase (Col(h)) that is thermally stable up to ca. 200 degrees C. The EDA interaction between porphycene and TCNQ has been probed using electronic and vibrational spectroscopy. A mixture of zinc(II) porphyrins, isomeric with the above porphycene complex, forms a rectangular columnar mesophase (Col(r)).     

Dilatometric investigation of thermotropic linear chain copper (II) alkanoates

The molar volumes of three binuclear copper (II) alkanoates (cupric octadecanoate, docosanoate, and tetracosanoate) were measured over the temperature range 30°–200 °C, which encompasses their phase transition to a columnar mesophase. A sharp volume increase in a narrow temperature interval about the transition was observed, consistent with a first-order phase transition. Values obtained for the partial molar volume of a methylene group in the columnar mesophase (16.9±0.3 cm³/mol) are between those for crystalline paraffins and for other smectic or discotic mesogens, respectively, indicating a disordered state, but not a complete fusion, of the aliphatic chains of the copper soaps in their columnar mesophase. The stacking period of the binuclear copper complexes in a column was derived from a combination of dilatometric and X-ray data. Its value, 4.64±0.08 Å, is independent of the chain length of the complex and of the temperature.     

Identification of a Peripheral Substitution Symmetry Effect in Self‐Assembled Architectures

Two complementary classes of molecules based on a triphenylene core are synthesized. The two‐dimensional (2D) assemblies of these molecules deposited on a highly oriented pyrolytic graphite (HOPG) surface are identified with scanning tunneling microscopy (STM). Structures with large cavities are formed by symmetric molecules, while uniform and closely packed stripe‐assembled structures are obtained for asymmetric molecules. X‐ray diffraction (XRD) results support the observation of an ordered hexagonal columnar mesophase for symmetric molecules and a rectangular columnar mesophase for asymmetric molecules. The study demonstrates that the substitution symmetry has significant effects on the assembly characteristics of molecular architectures and also on the three‐dimensional (3D) macroscopic properties of the molecular materials.     

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.     

A propeller-like uranyl metallomesogen

Uranyl triflate forms with three imidazo[4,5-f]-1,10-phenanthroline ligands a propeller-like complex that exhibits a hexagonal columnar phase. The ligand is not liquid-crystalline, but a mesophase is induced upon complex formation with the uranyl salt. The thermal behavior has been investigated by polarizing optical microscopy and by high-temperature X-ray diffraction. A model of the stacking of the molecules in the mesophase is proposed.     

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.     

Mesomorphic properties of a tetraphenylporphyrin metallomesogen with a weak hydrogen bond interaction between axial ligands: dihydroxo[5,10,15,20-tetrakis(4-n-dodecylphenyl)porphinato]silicon(IV)

A new metallomesogen, the dihydroxo[5,10,15,20-tetrakis(4-n-dodecylphenyl)porphinato]silicon(IV) complex, C₁₂TPPSi(OH)₂, was synthesized and its mesomorphism was investigated in terms of the axial hydrogen bond interaction in the stacked columnar structure. It was found that this compound exhibits a 3D plastic lamellar mesophase with a columnar structure, and the axial hydroxyl groups are connected by a very weak hydrogen bond interaction in the column. This causes a dramatic increase of the clearing point for the mesophase, even though the stacking periodicity is far larger (c. 9?Å) than that typically found for a columnar meosphase (c. 3.5?Å).     

Rational tuning of melting entropies for designing luminescent lanthanide-containing thermotropic liquid crystals at room temperature

The connection of twelve peripheral and divergent dodecyloxy chains to a central tridentate aromatic binding unit provides the dodecacatenar ligand L11, for which room-temperature mesomorphism is detected. An enthalpically unbalanced large melting entropy (DeltaSmL11=226 J mol(-1) K(-1)) results from the programmed microsegregation induced in the crystalline phase, a phenomenon which is maintained in the associated lanthanide complexes [Ln(L11)(NO3)3] and [Ln(L11)(CF3CO2)3]2. Low-temperature melting processes (-43相似文献   

Unusual mesomorphic behaviour of an ethynyl-substituted phthalocyanine

An ethynyl-substituted nickel(II) phthalocyanine has been synthesised and its thermotropic properties studied; optical microscopy, differential scanning calorimetry (DSC) and X-ray diffraction (XRD) techniques revealed an unusual mesomorphic behaviour observed for the first time in phthalocyanine systems where each disk of the hexagonal columnar mesophase is formed by two ethynyl-substituted phthalocyanine units.