Liquid Crystalline and Gel Properties of Luminescent Cyclometalated Palladium Complexes with Benzoylthiourea Ligands.

The design and development of new luminescent metallogels formed by cyclometalated palladium(II) complexes in protic solvents were investigated by a combination of differential scanning calorimetry (DSC), polarized optical microscopy (POM), and rheology. Cyclometalated palladium(II) complexes based on imine ligand and ancillary benzoylthiourea (BTU) ligand showed red emission in solid and gel states. The formation of a lyotropic liquid crystal phase was observed for the complex bearing shorter alkyl groups on the BTU ligand. This complex also behaved as a thermotropic liquid crystal that displays a monotropic smectic A phase (SmA). Dynamic rheology measurements (frequency sweep in the 5-90 °C range) of the 1-decanol solution of palladium(II) complexes highlighted their supramolecular self-association ability to generate 3D networks and form gels as a final result.

Columnar Liquid Crystals of Copper(I) Complexes with Ionic Conductivity and Solid State Emission.

Two neutral copper(I) halide complexes ([Cu(BTU)2X], X = Cl, Br) were prepared by the reduction of the corresponding copper(II) halides (chloride or bromide) with a benzoylthiourea (BTU, N-(3,4-diheptyloxybenzoyl)-N'-(4-heptadecafluorooctylphenyl)thiourea) ligand in ethanol. The two copper(I) complexes show a very interesting combination of 2D supramolecular structures, liquid crystalline, emission, and 1D ionic conduction properties. Their chemical structure was ascribed based on ESI-MS, elemental analysis, IR, and NMR spectroscopies (1H and 13C), while the mesomorphic behavior was analyzed through a combination of differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and powder X-ray diffraction (XRD). These new copper(I) complexes have mesomorphic properties and exhibit a hexagonal columnar mesophase over a large temperature range, more than 100 K, as evidenced by DSC studies and POM observations. The thermogravimetric analysis (TG) indicated a very good thermal stability of these samples up to the isotropization temperatures and over the whole temperature range of the liquid crystalline phase existence. Both complexes displayed a solid-state emission with quantum yields up to 8% at ambient temperature. The electrical properties of the new metallomesogens were investigated by variable temperature dielectric spectroscopy over the entire temperature range of the liquid crystalline phase. It was found that the liquid crystal phases favoured anhydrous proton conduction provided by the hydrogen-bonding networks formed by the NH…X moieties (X = halide or oxygen) of the benzoylthiourea ligand in the copper(I) complexes. A proton conductivity of 2.97 × 10-7 S·cm-1 was achieved at 430 K for the chloro-complex and 1.37 × 10-6 S·cm-1 at 440K for the related bromo-complex.

Editorial: Special Issue "Liquid Crystals 2020".

This Special Issue, entitled "Liquid Crystals 2020", is a collection of ten original research papers, including two feature papers, on theoretical and experimental advanced studies of liquid crystal science and technology [...].

Novel Gemini Surfactant for Binding Eu(III)-Polyoxometalate into Hydrogels and Polymer Latexes.

The incorporation of rare-earth ions into polymer matrices can lead to useful materials in various fields such as biomarkers, lasers, luminescent devices, optical storage materials, and so on. Methods of incorporation are either extremely simple, such as mixing the polymer and the ion of interest in adequate solvents, or more sophisticated such as synthesizing predesigned monomers that contain the rare-earth ion or binding the ion on an already formed polymer chain. Cationic gemini surfactants represent a class of surfactants that can be used to incorporate metal-oxygen cluster compounds by means of strong electrostatic interactions. In this study, first, a novel cationic gemini surfactant having double bonds on both side chains was designed and prepared. After characterization, the surfactant was used to synthesize hydrogels with different degrees of crosslinking and also as a surfmer in emulsion polymerization of methyl methacrylate. The resulted polymer matrices were able to bind europium-polyoxometalate Na9[EuW10O36].32H2O. In case of luminescent lanthanide ions, changing the microenvironment around the metal ion also changes the intensity of some emission peaks as well as other luminescent parameters. Investigation of emission spectra of Eu3+ indicates a decrease in the symmetry of the microenvironment, when the polyanions pass from water to latex, to surfactant solution, and to hydrogel.

3D Porous Collagen Matrices-A Reservoir for In Vitro Simultaneous Release of Tannic Acid and Chlorhexidine.

The treatment of wounds occurring accidentally or as a result of chronic diseases most frequently requires the use of appropriate dressings, mainly to ensure tissue regeneration/healing, at the same time as treating or preventing potential bacterial infections or superinfections. Collagen type I-based scaffolds in tandem with adequate antimicrobials can successfully fulfill these requirements. In this work, starting from the corresponding hydrogels, we prepared a series of freeze-dried atelocollagen type I-based matrices loaded with tannic acid (TA) and chlorhexidine digluconate (CHDG) as active agents with a broad spectrum of antimicrobial activity and also as crosslinkers for the collagen network. The primary aim of this study was to design an original and reliable algorithm to in vitro monitor and kinetically analyze the simultaneous release of TA and CHDG from the porous matrices into an aqueous solution of phosphate-buffered saline (PBS, pH 7.4, 37 °C) containing micellar carriers of a cationic surfactant (hexadecyltrimethylammonium bromide, HTAB) as a release environment that roughly mimics human extracellular fluids in living tissues. Around this central idea, a comprehensive investigation of the lyophilized matrices (morpho-structural characterization through FT-IR spectroscopy, scanning electron microscopy, swelling behavior, resistance against the collagenolytic action of collagenase type I) was carried out. The kinetic treatment of the release data displayed a preponderance of non-Fickian-Case II diffusion behavior, which led to a general anomalous transport mechanism for both TA and CHDG, irrespective of their concentrations. This is equivalent to saying that the release regime is not governed only by the gradient concentration of the releasing components inside and outside the matrix (like in ideal Fickian diffusion), but also, to a large extent, by the relaxation phenomena of the collagen network (determined, in turn, by its crosslinking degree induced by TA and CHDG) and the dynamic capacity of the HTAB micelles to solubilize the two antimicrobials. By controlling the degree of physical crosslinking of collagen with a proper content of TA and CHDG loaded in the matrix, a tunable, sustainable release profile can be obtained.

Synthesis and characterization of novel acylthiourea compounds used in ions recognition and sensing in organic media.

A series of novel N-acyl-N'-aryl thiourea derivatives were designed and prepared with the aim to develop dual responsive receptors for anions and cations. The structure of the new products was confirmed by NMR spectroscopy (13C and 1H), elemental analysis, and IR spectroscopy. Their thermal stability was studied by thermogravimetric analysis (TG) and it was found that these acyl thiourea derivatives are stable up to 160 °C. The ion recognition and sensing properties of the acyl thiourea compounds were investigated by UV-VIS absorption spectroscopy in organic media upon the addition of various salts. The UV-VIS studies revealed that these acyl thiourea derivatives are able to sense biological important ions such as fluoride and copper (II) ions.

Thermal and Emission Properties of a Series of Lanthanides Complexes with N-Biphenyl-Alkylated-4-Pyridone Ligands: Crystal Structure of a Terbium Complex with N-Benzyl-4-Pyridone.

This work focuses on the investigation of the liquid crystalline behavior and luminescence properties of the lanthanide complexes of Eu(III), Sm(III) and Tb(III) with N-biphenyl-alkylated-4-pyridone ligands. The organic ligands having a biphenyl group attached via a long flexible spacer with either 9 or 10 carbon atoms were synthesized by the reaction between 4-hydroxypyridine and the corresponding bromide compounds. The chemical structures of the organic and lanthanide complexes were assigned based on elemental analysis, single-crystal X-ray diffraction, 1H, 13C NMR and IR spectroscopies, and thermogravimetric analysis (TGA). The X-ray diffraction analysis of a parent compound shows that the lanthanide ions are surrounded by three monodentate pyridone ligands and three bidentate nitrate ions, giving a 9-coordinate environment. The mesogenic behavior and the type of liquid crystalline phases exhibited by the new complexes were analyzed by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM), and powder X-ray diffraction (XRD) studies. Only the lanthanide complexes with longer spacer (10) display a monotropic SmA phase, typically on a short thermal range (less than 10 °C). The complexes with shorter flexible chains (9) show no liquid crystalline properties with melting temperatures lower than their analogs with longer spacers. The emission spectra recorded in solid state at room temperatures show typical emission bands for each lanthanide ion employed (Eu(III), Tb(III) and Sm(III)).

Wide-Range Columnar and Lamellar Photoluminescent Liquid-Crystalline Lanthanide Complexes with Mesogenic 4-Pyridone Derivatives.

A series of liquid crystals with various lanthanide ions (EuIII , SmIII , and TbIII ) was designed and prepared starting from the corresponding lanthanide nitrates and N-alkylated 4-pyridone derivatives bearing mesogenic 3,4,5-tris(alkyloxy)benzyl moieties (alkyl=hexyl, octyl, decyl, dodecyl, tetradecyl, or hexadecyl). These new lanthanidomesogens were investigated for their mesogenic properties by a combination of differential scanning calorimetry, polarizing optical microscopy, and temperature-dependent powder X-ray diffraction (XRD). Their thermal stability was assessed by thermogravimetric analysis. All of these complexes show enantiotropic liquid-crystalline behavior with lamellar (SmA) phases in the case of shorter-chain complexes (C6 and C8 ) or hexagonal columnar phases (Colh ) for complexes with longer alkyl chains (C12 , C14 , and C16 ), which were assigned on the basis of their characteristic textures and XRD studies. For complexes with an intermediate number of carbon atoms in the side chains (C10 ), both a lamellar phase at lower temperatures and a Colh phase at higher temperatures were evidenced. In the solid state, all these complexes show characteristic emissions assigned to the corresponding lanthanide ion. In addition, the luminescence decay curves showed single-exponential decays with characteristic times in the millisecond range (0.75-0.90 ms for EuIII , 0.045-0.060 ms for SmIII , and 0.75-1.05 ms for TbIII ).

Dielectric properties of a bisimidazolium salt with dodecyl sulfate anion doped with carbon nanotubes.

A new bisimidazolium salt with dodecyl sulfate as counterion has been designed and prepared. This salt shows a SmA phase that is stable at room temperature. The new ionic liquid crystal (ILC) was characterized by 1H NMR, 13C NMR and IR spectroscopy. Its liquid crystalline properties were analyzed by polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and powder X-ray diffraction (XRD) studies. The dielectric spectra of the ILC doped with different concentrations of carbon nanotubes (CNT) were recorded over a wide frequency and temperature range of 10-1 to 107 Hz and 293-338 K, respectively. The values of the activation energy were found in the range of 0.46-0.61 eV; the characteristic time was obtained by fitting the spectra of the dielectric loss with the Havriliak-Negami functions. As a result of doping the ILC with CNT, the electric conductivity increases significantly. Ionic conductivity is dominant and it was indirectly observed through the electrode polarization (EP) effect. The very high dielectric permittivity values and the decrease of the electric conductivity at low frequencies confirm the presence of EP.

From Mesomorphic Phosphine Oxide to Clustomesogens Containing Molybdenum and Tungsten Octahedral Cluster Cores.

New clustomesogens (i.e., metal atom clusters containing liquid crystalline (LC) materials) have been obtained by grafting neutral cyanobiphenyl (CB)- or cholesteryl-containing tailor-made dendritic mesomorphic triphenylphosphine oxide ligands on luminescent (M6 Cl(i) 8 )(4+) octahedral cluster cores (M=Mo, W). The LC properties were studied by a combination of polarizing optical microscopy (POM), differential scanning calorimetry (DSC), and X-ray powder diffraction analyses. While the organic ligands showed various mesophase types ranging from nematic, SmA columnar (SmACol ), SmA, and SmC phases, it turned out that the corresponding clustomesogens formed layered phases (SmA) over a wide range of temperatures that depend on the nature and density of mesogenic groups employed. Intrinsic luminescence properties of the cluster precursors are preserved over the entire range of LC phase existence.

A new class of thermotropic lanthanidomesogens: Eu(III) nitrate complexes with mesogenic 4-pyridone ligands.

A new class of thermotropic lanthanidomesogens has been designed and prepared. They are based on 4-pyridone ligands that possess mesogenic cyanobiphenyl groups attached to the 4-pyridone unit via a flexible long alkyl spacer and show a very high thermal stability (decomposition temperatures near 300 °C). Depending on the alkyl length spacer, these complexes exhibit a SmA phase with transition temperatures influenced by the number of mesogenic groups employed and the spacer length.

Voltage-driven photoluminescence modulation of liquid-crystalline hybridized ZnO nanoparticles.

Liquid-crystalline hybrid nanomaterials have been obtained by grafting mesogenic units around luminescent ZnO nanocrystals of 5 nm in diameter. Modifying the mesogenic density around the inorganic core allows the modulation of the liquid-crystalline behavior and its miscibility in commercial liquid crystal (LC). The strong blue photoluminescence observed for the hybrids can be modulated by applying a voltage on a LC cell containing commercial LC and 10 wt % of hybrid.

Thermotropic luminescent clustomesogen showing a nematic phase: a combination of experimental and molecular simulation studies.

Octahedral Mo6 nanoclusters are functionalized with two organic ligands containing cyanobiphenyl (CB) units, giving luminescent hybrid liquid crystals (LC). Although the mesogenic density around the bulky inorganic core is constant, the two hybrids show different LC properties. Interestingly, one of them shows a nematic phase, which is particularly rare for this kind of supermolecular system. This surprising result is explained by using large-scale molecular dynamic simulations.

Luminescent liquid crystalline materials based on palladium(II) imine derivatives containing the 2-phenylpyridine core.

In this work we report our studies concerning the synthesis and characterisation of a series of imine derivatives that incorporate the 2-phenylpyridine (2-ppy) core. These derivatives were used in the cyclometalating reactions of platinum(II) or palladium(II) in order to prepare several complexes with liquid crystalline properties. Depending on the starting materials used as well as the solvents employed, different metal complexes were obtained, some of them showing both liquid crystalline behaviour and luminescence properties at room temperature. It was found that, even if there are two competing coordination sites, the cyclometalation process takes place always at the 2-ppy core with (for Pt) or without (for Pd) the imine bond cleavage. We successfully showed that it is possible to prepare emissive room temperature liquid crystalline materials based on double cyclopalladated heteroleptic complexes by varying the volume fraction of the long flexible alkyl tails on the ancillary benzoylthiourea (BTU) ligands.

Liquid crystal properties resulting from synergetic effects between non-mesogenic organic molecules and a one nanometre sized octahedral transition metal cluster.

This work presents the synthesis and studies of a red-NIR luminescent liquid crystal compound based on an octahedral metallic cluster core orthogonally bounded to six non-mesogenic organic ligands. It evidences synergetic effects between the organic and inorganic parts of the hybrid, resulting in the generation of liquid crystal properties on cooling from the isotropic melt.

Selective functionalisation of Re6 cluster anionic units: from hexa-hydroxo [Re6Q8(OH)6]4- (Q = S, Se) to neutral trans-[Re6Q8L4L'2] hybrid building blocks.

The reaction of [Re6Q(i)8(OH)(a)6]4- (Q = S, Se) with p-tert-butylpyridine (TBP) in water leads to neutral trans-[Re6Q8(TBP)4(OH)2] whose hydroxyl reactivity with carboxylic acid and TBP exchange reaction with functional pyridine have been investigated.

Reaction of bis(phosphine)(hydrotris(3,5-dimethylpyrazolyl)borato)rhodium(I) with phenylacetylene, p-nitrobenzaldehyde, and triphenyltin hydride: structures of [Rh(Tp)(PPh(3))(2)], [Rh(Tp)(H)(C(2)Ph)(P(4-C(6)H(4)F)(3))], [Rh(Tp)(H)(COC(6)H(4)-4-NO(2))(PPh(3))], and [Rh(Tp)(H)(SnPh(3))(PPh(3))].

The complexes [Rh(Tp)(PPh(3))(2)] (1a) and [Rh(Tp)(P(4-C(6)H(4)F)(3))(2)] (1b) combine with PhC(2)H, 4-NO(2)-C(6)H(4)CHO and Ph(3)SnH to give [Rh(Tp)(H)(C(2)Ph)(PR(3))] (R = Ph, 2a; R = 4-C(6)H(4)F, 2b), [Rh(Tp)(H)(COC(6)H(4)-4-NO(2))(PR(3))] (R = Ph, 3a), and [Rh(Tp)(H)(SnPh(3))(PR(3))] (R = Ph, 4a; R = 4-C(6)H(4)F, 4b) in moderate to good yield. Complexes 1a, 2b, 3a, and 4a have been structurally characterized. In 1a the Tp ligand is bidentate, in 2b, 3a, and 4a it is tridentate. Crystal data for 1a: space group P2(1)/c; a = 11.9664(19), b = 21.355(3), c = 20.685(3) A; beta = 112.576(7) degrees; V = 4880.8(12) A(3); Z = 4; R = 0.0441. Data for 2b: space group P(-)1; a = 10.130(3), b = 12.869(4), c = 17.038(5) A; alpha = 78.641(6), beta = 76.040(5), gamma = 81.210(6) degrees; V = 2100.3(11) A(3); Z = 2; R = 0.0493. Data for 3a: space group P(-)1; a = 10.0073(11), b = 10.5116(12), c = 19.874(2) A; alpha = 83.728(2), beta = 88.759(2), gamma = 65.756(2) degrees; V =1894.2(4) A(3); Z = 2; R = 0.0253. Data for 4a: space group P2(1)/c; a = 15.545(2), b = 18.110(2), c = 17.810(2) A; beta = 95.094(3) degrees; V = 4994.1(10) A(3); Z = 4; R = 0.0256. NMR data ((1)H, (31)P, (103)Rh, (119)Sn) are also reported.