Enhancement of smectic C mesophase stability by using branched alkyl chains in the auxiliary ligands of luminescent Pt(II) and Pd(II) complexes.

International audienceA novel series of Pd(II) and Pt(II) complexes based on cyclometallated imine ligands and N-benzoylthiourea (BTU) derivatives as auxiliary ligands has been prepared and their liquid crystalline properties as well as photophysical properties have been investigated. The crystal structure of one cyclometallated Pt(II) complex with N-(p-F-phenyl)-N'-benzoylthiourea as a co-ligand has been solved. The liquid crystalline properties have been investigated by a combination of DSC, POM and variable temperature powder X-ray diffraction. These new metallomesogens display either a monotropic SmC phase or both SmA and SmC phases, depending on the number of alkoxy groups attached to the imine ligand, alkyl chain length or the use of branched alkoxy terminal groups. We found that the introduction of branched alkoxy terminal groups lead to lower transition temperatures and stabilization of the SmC phase in both the Pd(II) and Pt(II) complexes. While the Pd(II) complexes display no emission, the Pt(II) complexes show good emission properties in solution, in the solid state and as a PMMA film at room temperature, and their investigation is reported

Refinement of Magnetite Nanoparticles by Coating with Organic Stabilizers

Magnetite nanoparticles are of great importance in nanotechnology and nanomedicine and have found manifold applications. Here, the effect of coating of magnetite nanoparticles with organic stabilizers, such as O-phosphoryl ethanolamine, glycerol phosphate, phospho-l-ascorbic acid, phospho-d,l-serine, glycolic acid, lactic acid, d,l-malic acid, and d,l-mandelic acid was studied. Remarkably, this procedure led to an improvement of saturation magnetization in three cases rather than to an unfavorable decrease as usually observed. Detailed X-ray powder diffraction investigations revealed that changes in the average crystallite occurred in the coating process. Surprisingly, changes of the average crystallite sizes in either direction were further observed, when the exposure time to the stabilizer was increased. These results imply a new mechanism for the well-known coating of magnetite nanoparticles with stabilizers. Instead of the hitherto accepted simple anchoring of the stabilizers to the magnetite nanoparticle surfaces, a more complex recrystallization mechanism is likely, wherein partial re-dispersion of magnetite moieties from the nanoparticles and re-deposition are involved. The results can help producers and users of magnetite nanoparticles to obtain optimal results in the production of core shell magnetite nanoparticles

Evidence of Counterion Size Effect on the Stability of Columnar Phase of Ionic Liquid Crystals Based on Pyridinium Salts Derived from <i>N</i>-3,4,5-Tri(alkyloxy)-benzyl-4-pyridones

The synthesis and characterization of novel ionic liquid crystals based on pyridinium salts with Br− and PF6− counterions are described in this work. These pyridinium salts were derived from 4-hydroxypyridine, both by N- and O-alkylation. The 3,4,5-tri(alkyloxy)-benzyl mesogenic unit was attached to the nitrogen atom of the pyridinium ring. Alkyl chains with a different number of carbon atoms (6, 8, 10, 12 and 14) were employed in order to show the effect on the stability of mesophase. The POM (polarizing optical microscopy) and XRD (powder X-ray diffraction) studies indicated that bromide salts with shorter chains C6, C8 and C10 do not show mesomorphic properties, while longer chain analogues with C12 and C14 exhibit two enantiotropic columnar phases. Surprisingly, the pyridinium salts with the larger size PF6− counterion do not exhibit liquid crystal properties

Synthesis and stereochemistry of some new 1,3,5-tris(1,3-dioxan-2-yl)-benzene derivatives

International audienceThe synthesis and the stereochemistry of new 1,3,5-tris(1,3-dioxan-2-yl)-benzene derivatives are reported. The anancomeric structure and the axial orientation of the aryl group with respect to all 1,3-dioxane rings, and the cis-trans isomerism of some of the compounds are revealed. The data are supported by NMR investigations and by the molecular structure of one compound determined by single crystal X-ray diffractometry

Evidence of Counterion Size Effect on the Stability of Columnar Phase of Ionic Liquid Crystals Based on Pyridinium Salts Derived from N-3,4,5-Tri(alkyloxy)-benzyl-4-pyridones

The synthesis and characterization of novel ionic liquid crystals based on pyridinium salts with Br&minus; and PF6&minus; counterions are described in this work. These pyridinium salts were derived from 4-hydroxypyridine, both by N- and O-alkylation. The 3,4,5-tri(alkyloxy)-benzyl mesogenic unit was attached to the nitrogen atom of the pyridinium ring. Alkyl chains with a different number of carbon atoms (6, 8, 10, 12 and 14) were employed in order to show the effect on the stability of mesophase. The POM (polarizing optical microscopy) and XRD (powder X-ray diffraction) studies indicated that bromide salts with shorter chains C6, C8 and C10 do not show mesomorphic properties, while longer chain analogues with C12 and C14 exhibit two enantiotropic columnar phases. Surprisingly, the pyridinium salts with the larger size PF6&minus; counterion do not exhibit liquid crystal properties