Effects of ions on the liquid crystalline mesophase of transition-metal salt: Surfactant (CnEOm)

The transition-metal aqua complex salts [M(H2O) x]Y2 (where M is some of the first- and second-row transitionmetal ions and Y is Cl-, NO3-, and ClO4- counteranions) form liquid crystalline (LC) mesophases with oligo(ethylene oxide) nonionic surfactants (CnH 2n+1(CH2CH2O)mOH, denoted as C nEOm). The structure of the [M(H2O) x]Y2:CnEOm mesophase is usually 2D hexagonal in nitrate systems, cubic in perchlorate systems, and absent in the chloride systems. The solubility of the metal aqua complex salt follows the Hofmeister series in a [M(H2O)x]Y2:C nEOm mesophase. However, the nitrate ion interacts with the metal center as a bidentate and/or unidentate ligand, therefore reducing the ion density (and/or ionic strength) of the LC medium and further enhancing the solubility of nitrate salt in the LC systems. The cobalt chloride salt is the only soluble chloride salt that undergoes ligand-exchange reactions in the [Co(H2O)6]Cl2:CnEOm system. In an LC mesophase, anions have a greater influence on the hydrophilicity of nonionic surfactants than do cations. The structure and stability of the LC mesophase can be controlled by controlling either the hydrophilicity of the nonionic surfactant (by choosing the right anion type) or the ion density of the medium (by either influencing the equilibrium between the free and coordinated anions or balancing between the coordinating and noncoordinating anions in the medium)

Lyotropic liquid-crystalline phase of oligo(ethylene oxide) surfactant/transition metal salt and the synthesis of mesostructured cadmium sulfide

Lyotropic liquid-crystalline (LLC), transition metal salt: oligo(ethylene oxide) nonionic surfactant (CnH2n+1(CH2CH2O)mOH, denoted as CnEOm), systems have been studied by means of diffraction, microscopy, and spectroscopy to elucidate the structural, thermal, and templating properties. In the system, the lyotropic salts of transition metal aqua complexes, such as chlorides and sulfates, are insoluble and do not form a LC phase in CnEOm-type nonionic surfactants. However, the transition metal aqua complexes of nitrates and perchlorates are soluble and form 2D and 3D hexagonal and cubic mesophases. These phases are stable in a very broad range of salt:surfactant mole ratios (1.0 and 3.6). The nitrate salts form a hexagonal mesophase. However, in high nitrate salt concentrations (above 3.2 salt:surfactant mole ratio), the salt crystals are either insoluble or the salt:surfactant mixtures are in a cubic mesophase. The structure and thermal properties of the new system are determined by the solubility of the transition metal salts, the concentration of the salt, and the surfactant type. The LC [Cd(H2O)4](NO3)2: C12EO10 mesophase has been reacted with H2S gas to produce solid mesostructured CdS (meso-CdS). The meso-CdS particles are spherical in morphology and are made up of hierarchical organization of 2-4-nm CdS particles. The salt:surfactant LLC systems and the solid meso-CdS have been investigated using polarized optical microscopy, X-ray diffraction, Fourier transform infrared, Fourier transform Raman, and UV-vis absorption spectroscopy, scanning electron microscopy, and transmission electron microscopy