A biaxial nematic phase had been predicted with D(2h) symmetry, wherein the mesogen's long and short transverse axes are simultaneously aligned along the two orthogonal, primary and secondary directors, n and m, respectively. The unique low-angle x-ray diffraction patterns in the nematic phases exhibited by three rigid bent-core mesogens clearly reveal their biaxiality. The results of x-ray diffraction can be readily reproduced by ab initio calculations that explicitly include the bent-core shape in the form factor and assume short-range positional correlations.

Lyotropic chromonic liquid crystals (LCLCs) are formed by molecules with ionic groups at the periphery that associate into stacks through noncovalent self-assembly while in water. The very existence of the nematic (N) phase in the typical LCLC, the dye Sunset Yellow (SSY) is a puzzle, as the correlation length associated with the stacking, as measured in the X-ray experiments, is too short to explain the orientational order by the Onsager model. We propose that the aggregates can be more complex than simple rods and contain "stacking faults" such as junctions with a shift of neighboring molecules, 3-fold junctions, etc. We study how ionic additives, such as salts of different valency and pH-altering agents, alter the N phase of SSY purified by recrystallization. The additives induce two general trends: (a) stabilization of the N phase, caused by the mono and divalent salts (such as NaCl), and evidenced by the increase of the N-to-I transition temperature and the correlation length; (b) suppression of the N phase manifested in the decrease of the N-to-I transition temperature and in separation of the N phase into a more densely packed N phase or the columnar (C) phase, coexisting with a less condensed I phase. The scenario (b) can be triggered by simply increasing pH (adding NaOH). The effects produced by tetravalent spermine fall mostly into the category (b), but the detail depends on whether this additive is in its salt form or a free base form. The base form causes changes through changes in pH and possible excluded volume effects whereas the salt form might disrupt the structure of SSY aggregates.

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Dense multicomponent systems with macromolecules and small solutes attract a broad research interest as they mimic the molecularly crowded cellular interiors. The additives can condense and align the macromolecules, but they do not change the degree of covalent polymerization. We chose a lyotropic chromonic liquid crystal with reversibly and non-covalently assembled aggregates as a much softer system, reminiscent of ''living polymers'', to demonstrate that small neutral and charged additives cause condensation of aggregates with ensuing orientational and positional ordering and nontrivial morphologies of phase separation, such as tactoids and toroids of the nematic and hexagonal columnar phase coexisting with the isotropic melt. Scanning transmission X-ray microscopy (STXM) with near edge X-ray absorption fine structure (NEXAFS) analysis as well as fluorescent microscopy demonstrates segregation of the components. The observations suggest that self-assembly of chromonic aggregates in the presence of additives is controlled by both entropy effects and by specific molecular interactions and provide a new route to the regulated reversible assembly of soft materials formed by low-molecular weight components.

1-(2,6-Diisopropylphenyl)-4-(phenylthio/selenomethyl)-1H-1,2,3-triazole (L1/L2) was synthesized by a 'Click' reaction and treated with [Pd(CH3CN)2Cl2] for 5 h or [(η(6)-C6H6)RuCl(μ-Cl)]2 for 8 h (followed by reaction with NH4PF6) at room temperature, resulting in complexes [Pd(L)Cl2] (1 and 2) or [(η(6)-C6H6)Ru(L)Cl]PF6 (3 and 4) (L = L1 or L2), respectively. The four complexes (1-4) and ligands (L1 and L2) were characterized with (1)H, (13)C{(1)H} and (77)Se{(1)H} NMR spectroscopy and high resolution mass spectrometry. The single crystal structures of 1-4 were solved. The geometry of Pd in 1 and 2 is distorted square planar. The Pd-S and Pd-Se bond distances in 1 and 2 are 2.277(3) and 2.384(6) Å respectively. In 3 and 4, there is a pseudo-octahedral "piano-stool" type disposition of donor atoms around Ru. The Ru-S and Ru-Se bond lengths in 3 and 4 are 2.3728(12) and 2.4741(6) Å respectively. The catalytic activity of complexes 1 and 2 was explored for Suzuki-Miyaura coupling (SMC) in water and the Sonogashira coupling reaction. For various aryl bromides, including deactivated ones, complexes 1 and 2 were found to be efficient catalysts for both couplings. The optimum loading of 1 and 2 required to catalyze both coupling reactions is of the order of 0.001-2 mol% of Pd. For SMC, no additive or phase transfer catalyst was added. For catalysis of the transfer hydrogenation (TH) of aldehydes and ketones, the half-sandwich Ru(ii) complexes 3 and 4 were explored. Their optimum catalytic loading was found to be 0.1-0.4 mol% of Ru. For TH, both the water solvent and the glycerol hydrogen source are environmentally friendly. The catalytic efficiencies of 3 and 4 are comparable with those reported for other catalysts for TH carried out with 2-propanol or glycerol as a H-source. 1, with a sulfur ligand, is more efficient than 2 (Se analog) for both SMC and the Sonogashira coupling. The activities of 3 and 4 for TH are in the order Se > S.

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