Spontaneous chiral symmetry breaking in polar fluid-heliconical ferroelectric nematic phase.

Spontaneous mirror symmetry breaking by formation of chiral structures from achiral building blocks and emergent polar order are phenomena rarely observed in fluids. Separately, they have both been found in certain nematic liquid crystalline phases; however, they have never been observed simultaneously. Here, we report a heliconical arrangement of achiral molecules in the ferroelectric nematic phase. The phase is thus spontaneously both polar and chiral. Notably, the pitch of the heliconical structure is comparable to the wavelength of visible light, giving selective reflection controllable by temperature or application of a weak electric field. Despite bearing resemblance to the heliconical twist-bend nematic phase, this chiral ferroelectric nematic phase arises from electrical interactions that induce a noncollinear orientation of electric dipoles.

Ferroelectric Nematic-Isotropic Liquid Critical End Point.

A critical end point above which an isotropic phase continuously evolves into a polar (ferroelectric) nematic phase with an increasing electric field is found in a ferroelectric nematic liquid crystalline material. The critical end point is approximately 30 K above the zero-field transition temperature from the isotropic to nematic phase and at an electric field of the order of 10 V/µm. Such systems are interesting from the application point of view because a strong birefringence can be induced in a broad temperature range in an optically isotropic phase.

Chiral columns forming a lattice with a giant unit cell.

Mesogenic materials, quinoxaline derivatives with semi-flexible cores, are reported to form a new type of 3D columnar phase with a large crystallographic unit cell and Fddd lattice below the columnar hexagonal phase. The 3D columnar structure is a result of frustration imposed by the arrangement of helical columns of opposite chiralities into a triangular lattice. The studied materials exhibit fluorescence properties that could be easily tuned by modification of the molecular structure; for compounds with the extended π electron conjugated systems the fluorescence is quenched. For molecules with a flexible structure the fluorescence quantum yield reaches 25%. On the other hand, compounds with a more rigid mesogenic core, for which the fluorescence is suppressed, show effective photogeneration of charge carriers. For some materials bi-polar hole and electron transport was observed.

Calamitic and discotic liquid crystalline phases for mesogens with triangular cores.

Mesogenic compounds having new triangular mesogenic cores containing salicylaldimine and enaminocarbonyl or barbituric moieties have been synthesized and their liquid crystalline, dielectric and optical properties have been studied. Appropriate substitution of such cores with various numbers of lateral chains (alkoxy, perfluorinated or polyether) leads to mesogens forming either lamellar (SmC), nematic or columnar (Colhd and Colho) phases. Some of the materials show an unusual phase sequence with a re-entrant isotropic phase appearing below the columnar (Colhd) phase; others form two columnar hexagonal phases with a weakly first order transition between them. Also a new columnar superstructure with p2gg symmetry (Colros) was found, in which the crystallographic lattice is decorated with a two-molecule motive.

The first example of a mixed valence ternary compound of silver with random distribution of Ag(I) and Ag(II) cations.

The reaction between colourless AgSbF6 and sky-blue Ag(SbF6)2 (molar ratio 2 : 1) in gaseous HF at 323 K yields green Ag3(SbF6)4, a new mixed-valence ternary fluoride of silver. Unlike in all other Ag(I)/Ag(II) systems known to date, the Ag(+) and Ag(2+) cations are randomly distributed on a single 12b Wyckoff position at the 4̄ axis of the I4̄3d cell. Each silver forms four short (4 × 2.316(7) Å) and four long (4 × 2.764(6) Å) contacts with the neighbouring fluorine atoms. The valence bond sum analysis suggests that such coordination would correspond to a severely overbonded Ag(I) and strongly underbonded Ag(II). Thorough inspection of thermal ellipsoids of the fluorine atoms closest to Ag centres reveals their unusual shape, indicating that silver atoms must in fact have different local coordination spheres; this is not immediately apparent from the crystal structure due to static disorder of fluorine atoms. The Ag K-edge XANES analysis confirmed that the average oxidation state of silver is indeed close to +1⅓. The optical absorption spectra lack features typical of a metal thus pointing out to the semiconducting nature of Ag3(SbF6)4. Ag3(SbF6)4 is magnetically diluted and paramagnetic (µ(eff) = 1.9 µ(B)) down to 20 K with a very weak temperature independent paramagnetism. Below 20 K weak antiferromagnetism is observed (Θ = -4.1 K). Replacement of Ag(I) with potassium gives K(I)2Ag(II)(SbF6)4 which is isostructural to Ag(I)2Ag(II)(SbF6)4. Ag3(SbF6)4 is a genuine mixed-valence Ag(I)/Ag(II) compound, i.e. Robin and Day Class I system (localized valences), despite Ag(I) and Ag(II) adopting the same crystallographic position.

Dinuclear mesogens with antiferromagnetic properties.

Herein, two new groups of isomeric bimetallic nickel(II) and copper(II) complexes containing pyrazine or pyrimidine rings are synthesized and examined. The complexes exhibit liquid-crystalline columnar phases in a broad temperature range. For the copper(II) complexes, super-exchange coupling between two Cu(II) ions is observed. For the pyrimidine derivative in which the paramagnetic Cu(II) ions are separated only by three atoms, an antiferromagnetic spin alignment is detected. When the distance between Cu(II) ions increases to four atoms in the pyrazine derivative, the magnetic interaction becomes significantly weaker.

Fine-tuning of properties of bismacrocyclic dinuclear cyclidene receptors by N-methylation.

N-Methylated bismacrocyclic Cu and Ni complexes were synthesised and structurally characterised in the solid state. Their properties in solution were analysed by using NMR and ESR spectroscopies and electrochemical methods. Face-to-face biscyclidenes linked through polymethylene chains form rectangular boxlike cations. These moieties can host some small guest molecules (water, pi-electron donating compounds) and are stabilised by a shell of neighbouring counterions. For the bismacrocyclic dinuclear complexes containing two nickel or two copper ions, the intramolecular interactions between the metallic centres are strengthened through methylation of the macrocyclic components, as compared with the nonmethylated species. We report the electron coupling created by two unpaired electrons coming from two copper centres observed by ESR spectroscopy. Methylation weakens the electron-acceptor properties of the complexes, which leads to less effective binding of the pi-electron-donating guests. It also increases the stability of the lower oxidation states. In the case of the copper complexes, both Cu(II)/Cu(I) and Cu(II)/Cu(III) reversible one-electron transfers are seen in the voltammograms. These changes in properties are interpreted as the consequences of steric repulsion between the methyl substituents and the macrocyclic ring.

Re-entrant isotropic phase between lamellar and columnar mesophases.

Tetradental cis-enaminoketone Ni (II) complexes with different molecular shape have been synthesized. Intramolecular hydrogen bonds, which stiffen the mesogenic core and restrict rotation of some molecular parts, have been introduced in these compounds. In the case of molecules with two hydrogen bonds and alkoxy terminal chains filling the inner molecular space, the uncommon phase sequence Iso-D(h)-Iso(re)-SmA (series III-3) was detected. For the first time, it was observed that the isotropic re-entrant (Iso(re)) phase (short-range order) is separating the columnar (D) (high-temperature) and the lamellar (SmA) (low-temperature) phases, both revealing long-range ordered structures.