Propeller-like hydrogen-bonded banana-melamine complexes inducing helical supramolecular organizations

The results of the study presented here show a new example of the use of liquid crystals and the interactions involved in the mesomorphic state to build up complex molecular organizations. We have pursued a design strategy in which hydrogen bonding allows the combination of the pi-stacking tendency of melamine and the lateral interaction capability of V-shaped molecules, which has been extensively demonstrated through nematic, smectic, or columnar mesophases. This combination addresses the formation of columnar arrangements with inherent helical organization. In this work, nonmesomorphic as well as mesomorphic V-shaped acids, with a structure similar to banana liquid crystals, have been complexed to a 2,4,6-triamino-1,3,5-triazine derivative in a proportion 3 to 1, respectively. Hydrogen-bonded supramolecules whose formation and stability in solution have been proven by infrared and NMR techniques have been thus obtained. DOSY experiments have allowed us to assess in solution the presence of the complexes and their tetrameric composition. All the complexes display mesogenic ability, and their mesomorphic organization has been studied by X-ray diffraction and CD spectroscopy. Results allow us to propose a helical columnar model for the mesophase originated from a propeller-like conformation of the supramolecular complexes.     

Effects of nonmesomorphic substituted benzonitriles on the dielectric properties of cyanobiphenyl liquid crystals

The effects of the cyano-substituted aromatic nonmesomorphic additives N-(3,4-dicyanophenyl)-4′-nonyloxybenzamide (I), 3,4-dicyanophenyl-4′-nonyloxybenzoate (II), 3,4-dicyanophenyl-3′,4′,5′-tris-(4″-undecyloxyphenylbenzoate)benzoate (III), and 4-(6-hydroxyhexyloxy)benzonitrile (IV) on the dielectric properties of 4-hexyloxy-4′-cyanobiphenyl and a liquid-crystal mixture E3 were studied. Dielectric anisotropy, birefringence, and orientational ordering were studied to show that monocyano derivative IV most strongly increased the dielectric anisotropy of mesomorphic compositions because of its effective incorporation into the liquid crystal matrix.     

Supramolecular Columnar Liquid Crystals Formed by Hydrogen Bonding between a Clicked Star‐Shaped s‐Triazine and Benzoic Acids

A star‐shaped tris(triazolyl)triazine is shown to establish hydrogen‐bond interactions with polycatenar benzoic acids. The formation of hydrogen‐bonded triazine/acid complexes has been demonstrated both in solution and in bulk by different techniques. The complexes, mainly formed by nonmesogenic components, all show enantiotropic hexagonal columnar mesomorphism, which relies on the formation of hydrogen‐bond complexes in a triazine/acid ratio of 1:3. This approach combines the straightforward synthesis of a nonmesomorphic triazine core by click chemistry, and the preparation of a supramolecular complex, providing a much more convenient route than covalent synthesis to modify the periphery of triazine discotics and thus to modulate their functionality.     

Liquid crystalline complexes of 4-alkoxystilbazoles with silver 1,12-dodecylene disulphate

A new series of metal complexes of silver(I) 1,12-dodecylene disulphate with 4-alkoxystilbazole ligands has been synthesized. These difunctional silver stilbazole complexes are mesomorphic, showing a nematic phase at short chain lengths and SmA and SmC phases at longer chain lengths. The single crystal X-ray structure of the hexyloxy homologue shows a polymerized arrangement of sulphate-bridged dimers.     

Liquid‐crystalline thermosets from liquid‐crystalline epoxy resins containing bisazomethinebiphenylene mesogens in the central core: Copolymerization with a nonmesomorphic epoxy resin

A new series of liquid‐crystalline epoxy resins was synthesized, and their mesomorphic behavior was investigated with differential scanning calorimetry, polarized optical microscopy, and wide‐angle X‐ray scattering. These glycidylic compounds had central aromatic imine mesogens derived from benzidine and aliphatic spacers of up to 10 methylene units that linked the mesogens to the glycidylic groups. Crosslinking these monomers with primary aromatic diamines led to nematic networks, some of which contained crystal inclusions. However, through curing with tertiary amines as catalytic agents or through copolymerization with different proportions of the nonmesomorphic epoxy monomer and primary amines as crosslinking agents, smectic C organized thermosets were prepared when the spacers had at least four methylene carbons. When they had fewer than four, the networks were nematic. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3631–3643, 2004     

Stabilization and induction of discotic mesophases by trifluoroacetic acid

It is shown that trifluoroacetic acid (TFA) can form 1 1 molar complexes with alkyloxy discotic compounds, thereby enhancing their mesomorphic properties. In particular, when hexaalkyloxytriphenylenes (THEn) (n being the number of carbons per side chain) are crystallized from, or mixed with, TFA, complexes are formed which exhibit the Dho(Colho) mesophase, as do the neat THEn's, but with a broader range of thermal stability and a higher degree of order. The mesophases of these complexes are completely miscible with those of the neat compounds. Likewise, 1 1 mixtures of hexa-alkyloxytribenzocyclononene (TBCEn) and TFA yield complexes showing enhanced mesomorphic properties for the mesogenic homologues of this series and induced mesomorphism for the lower homologues, which in the neat form are not mesogenic. The mesomorphic properties of these TFA complexes with THEn (n=3-6) and with TBCEn (n=4-6) are investigated by means of optical microscopy, differential scanning calorimetry, X-ray diffraction and NMR spectroscopy. It is suggested that the enhancement of the mesomorphic properties is due to formation of oxonium ion complexes.     

Liquid crystalline heteronuclear complexes with a ferrocene-containing Schiffs base

A series of new heteronuclear complexes of a ferrocene-containing Schiffs base (LH) with Ni^II, Pd^II, V^IVO, and Fe^III as the central atoms has been obtained. PdL₂, VOL₂ FeL₂Cl, and [FeL₂]₂O complexes manifest liquid-crystalline properties and NiL₂ is nonmesomorphic. The structures of the complexes synthesized have been established by magnetic measurements and IR and ESR spectroscopy. All of them except PdL₂ are paramagnetic. The antiferromagnetic exchange interactions have been observed in the Fe^III complexes. The correlation of liquid-crystalline properties with the geometry of the chelate centers is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 941–945, May, 1994.     

Alkali cation induced liquid crystalline properties of an oligophenylenevinylene-benzocrown ether conjugate

An oligophenylenevinylene-benzocrown ether conjugate has been prepared and its binding selectivity for alkali metal ions evaluated by electrospray mass spectrometry. Whereas this benzocrown-ether derivative does not exhibit any liquid crystalline properties, the self-assembly by coordination to potassium or cesium leads to supramolecular sandwich complexes with mesomorphic properties.     

Achiral banana-shaped mesogenic bidentate ligands and their Cu(II) and Pd(II) complexes

The first achiral bent-core banana-shaped bidentate ligands and their Cu(II) and Pd(II) metal complexes have been synthesized and investigated for mesomorphic behaviour. The bidentate ligands exhibit only one enantiotropic mesophase. The ligand having C 6 -alkoxy chains shows a mesophase that has been assigned as a two-dimensional B 1 phase while the C 8 and C 10 homologues stabilize the fluid B 2 mesophase showing antiferroelectric switching characteristics. In constrast, their corresponding Cu(II) and Pd(II) metal complexes are non-mesomorphic.     

Achiral banana-shaped mesogenic bidentate ligands and their Cu(II) and Pd(II) complexes

The first achiral bent-core banana-shaped bidentate ligands and their Cu(II) and Pd(II) metal complexes have been synthesized and investigated for mesomorphic behaviour. The bidentate ligands exhibit only one enantiotropic mesophase. The ligand having C6 -alkoxy chains shows a mesophase that has been assigned as a two-dimensional B1 phase while the C8 and C10 homologues stabilize the fluid B2 mesophase showing antiferroelectric switching characteristics. In constrast, their corresponding Cu(II) and Pd(II) metal complexes are non-mesomorphic.     

Silver pyrazolates as coordination-polymer luminescent metallomesogens

Silver pyrazolates with columnar liquid-crystal phases that are stable at room temperature have been prepared by reaction of silver nitrate with 3,5-diarylpyrazolates. The complexes consist of open-chain oligomers, despite the fact that the most common structural type for homoleptic coinage metal pyrazolates is the trimeric metallacycle [M(μ-pz)](3). The special characteristics of silver in forming reversible metal-ligand bonds in solution, evidenced experimentally, leads to supramolecular organizations in which the silver cations promote self-organization of the nonmesomorphic pyrazolates into helical 1D polymers that exhibit columnar mesophases. The materials are readily soluble in common organic solvents and are liquid-crystalline over a broader temperature range than their gold counterparts, which are known to form discrete cyclic trinuclear species. Thin films of the silver complexes show luminescence at room temperature. The compounds described here are the first examples of luminescent metallomesogens formed by a main-chain coordination polymer.     

On the reported mesomorphism of lanthanide complexes containing the hemicyanine structural unit

Close examination of the thermal behaviour of the (E)-N-hexadecyl-4-N', N'-dimethylaminostilbazolium tetrakis(1-phenyl-3-methyl-4-benzoyl-5-pyrazolonato)lanthanide(III) complexes has revealed that these compounds are not mesomorphic, in contradiction to an earlier report in the literature (K. Z. Wang et al., 1995, Solid State Commun. 95, 223). By replacing the bromide of the hemicyanine precursor (see the scheme) by a tetrakis(beta-diketonato)lanthanide(III) anion, new complexes were synthesized, but none shows a mesophase. Reasons for the absence of mesomorphism are discussed. Transition temperatures for the mesomorphic hemicyanine bromides are reported.     

Playing with PtII and ZnII Coordination to Obtain Luminescent Metallomesogens

Blue–green luminescent terpyridine-containing Pt^II and Zn^II complexes are reported. Equipped with lipophilic gallate units, which act as monodentate ancillary coordinating ligands and/or as anions, they display low-temperature mesomorphic properties (lamello-columnar and hexagonal mesophases for Pt^II and Zn^II complexes, respectively). The mesomorphic properties were investigated by polarised optical microscopy, differential scanning calorimetry, thermogravimetric analysis and X-ray scattering of bulk materials and oriented thin films. The model of self-assembly into the lamello-columnar phase of the Pt^II complex has been described in detail. The optical properties of the complexes were investigated in the liquid and condensed liquid crystalline states, highlighting the delicate balance between the role of the metal in determining the type of excited state responsible for the emission, and the role of the ancillary ligand in driving intermolecular interactions for proper mesophase formation.     

Supramolecular liquid crystals induced by intermolecular hydrogen bonding between benzoic acid and 4-(alkoxyphenylazo) pyridines

Supramolecular liquid crystalline complexes have been obtained from binary mixtures of 4-(alkoxyphenylazo) pyridines and 4-octyloxylbenzoic acid. None of the pyridine-based derivatives is mesomorphic, but the hydrogen-bonded complexes are. Their liquid crystalline properties were investigated by DSC, polarizing optical microscopy, FTIR spectroscopy and powder X-ray diffraction. The complexes exhibit enantiotropic smectic C phases.     

Supramolecular liquid crystals induced by intermolecular hydrogen bonding between benzoic acid and 4-(alkoxyphenylazo) pyridines

Supramolecular liquid crystalline complexes have been obtained from binary mixtures of 4-(alkoxyphenylazo) pyridines and 4-octyloxylbenzoic acid. None of the pyridine-based derivatives is mesomorphic, but the hydrogen-bonded complexes are. Their liquid crystalline properties were investigated by DSC, polarizing optical microscopy, FTIR spectroscopy and powder X-ray diffraction. The complexes exhibit enantiotropic smectic C phases.     

Columnar metallomesogens based on vanadyl(VI) and cobalt(II) complexes of N,N'-bis[3-(3,4-dialkoxyphenyl)3-oxopropenyl]ethylenediamines

The preparation, characterization and mesomorphic properties of vanadyl(VI) and cobalt(II) complexes derived from N , N -bis[3-(3,4-dialkoxyphenyl)-3-oxopropenyl]ethylenediamines are described. These half-disk-shaped molecules exhibited columnar mesophases over a wide range of temperature, as characterized by DSC analysis and polarizing optical microscopy. The structure of the mesophases was also confirmed as columnar hexagonal (Col_ho) by powder XRD. The vanadyl complexes were found to have substantially higher clearing temperatures and wider mesophase temperatures than the analogous cobalt complexes. The influence of the metal centres on the mesomorphic temperatures may be attributed to better intermolecular dative association in the vanadyl complexes than in the cobalt complexes.     

Columnar metallomesogens based on vanadyl(VI) and cobalt(II) complexes of N,N'-bis[3-(3,4-dialkoxyphenyl)3-oxopropenyl]ethylenediamines

The preparation, characterization and mesomorphic properties of vanadyl(VI) and cobalt(II) complexes derived from N, N -bis[3-(3,4-dialkoxyphenyl)-3-oxopropenyl]ethylenediamines are described. These half-disk-shaped molecules exhibited columnar mesophases over a wide range of temperature, as characterized by DSC analysis and polarizing optical microscopy. The structure of the mesophases was also confirmed as columnar hexagonal (Col_ho) by powder XRD. The vanadyl complexes were found to have substantially higher clearing temperatures and wider mesophase temperatures than the analogous cobalt complexes. The influence of the metal centres on the mesomorphic temperatures may be attributed to better intermolecular dative association in the vanadyl complexes than in the cobalt complexes.     

Magnetomesogens: Bis(1,3-di(4'-decoxyphenyl)propane-1,3-dionato)oxovanadium (IV)

β-Diketonate complexes of oxovanadium (IV) have been synthesized and their mesomorphic behaviour investigated. The title complex exhibits a short range monotropic columnar discotic phase, identified by its optical texture and by miscibility studies. The optical texture of the phase is retained on cooling to the crystal. As a consequence of the unpaired electron on vanadium the complexes are paramagnetic.     

Di[2-(4-substituted-phenyl)-3-mercapto-propenato]-nickel(II) complexes. Metallo-mesogens exhibiting broad nematic ranges

Di[2-(4-substituted-phenyl)-3-mercapto-propenato]-nickel(II) complexes have been synthesized and investigated. All of them are mesomorphic; they have nematic phases with wide ranges and typical Schlieren textures.     

Mesomorphism of complexed 2,6-disubstituted pyridine ligands: crystal and molecular structure of two bent-core pyridines

Bent-core, polycatenar pyridines are reported, synthesized via a Siegrist coupling of di- and tri-alkoxybenzylidene fragments with 2,6-dimethylpyridine. None of these pyridines was liquid crystalline. Isomeric materials based on a 3,5-disubstituted pyridine core were mesomorphic in hydrogen-bonded complexes, whereas these new materials were not. However, the new pyridines did form mesomorphic metal complexes with silver salts. Some insight into this behaviour is gleaned from single crystal structure determinations of the model systems, 3,5-bis(3',4'-dimethoxystyryl)pyridine and 2,6-bis(3',4'-dimethoxystyryl)pyridine.