Browsing by Subject "Transition metal compounds"

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Open Access
Phase separation in liquid crystalline mesophases of [Co(H 2O)6]X2: P65 Systems (X = NO3-, Cl-, or ClO4-)
(2007) Albayrak, C.; Gülten, G.; Dag, Ö.
Transition-metal aqua complex salts [M(H2O)6]X 2 (where M is Mn(II), Co(II), Ni(II), Zn(II), or Cd(II) and X is NO3-, Cl-, or ClO4-) can be dissolved in triblock poly(ethylene oxide) - poly(propylene oxide) - poly(ethylene oxide) copolymers (Pluronics, such as P65) to form homogeneous liquid crystalline (LC) mesophases. However, the [Co-(H2O) 6]X2:P65 LC mesophases slowly undergo phase separation into a disordered ion-free phase and an ordered ion-rich LC mesophase. The phase separation also takes place in the two-salt systems [Co(H2O) 6](NO3):[Co(H2O)6]-(ClO 4)2:P65 in which the ion-free disordered domains separate out from the initially ordered homogeneous mesophase. The phase separation results in a physical mixture of a hexagonal nitrate-rich and cubic perchlorate-rich LC and disordered ion-free domains in the mixed salt systems. The driving force in the phase separation in the [Co(H2O) 6]-X2:P65 system is Co(II)-catalyzed aerobic oxidation of P65 into ester and/or other oxidation products. The separation of ions in the [Co(H2O)6](NO3)2:[Co(H 2O)6](ClO4)2:P65 system is related to the mesostructures of the two-salt systems that are different, hexagonal in the [Co(H2O)6](NO3)2:P65 system and cubic in the [Co(H2O)6](ClO4)2:P65 system. There is no visible phase separation in the other transition-metal salt:P65 systems. The phase separation in the [Co-(H2O) 6]X2:P65 systems can also be eliminated by keeping the mesophase under a N2 atmosphere. © 2007 American Chemical Society.
Open Access
Synthesis of mesostructured metal sulfide films using [M(H2O)n](NO3)2:P85 (M = Cd(II) and Zn(II)) liquid crystalline mesophases
(2008) Türker, Y.; Dag, Ö.
Transition metal salt-pluronic liquid crystalline (TMS-PLC) mesophases of A-P85, B-P85 and ((1 - x)A + xB)-P85 (where A is [Cd(H2O) 4](NO3)2, B is [Zn(H2O) 6](NO3)2 and P85 is a triblock copolymer, HO(CH2CH2O)26(CH2(CH 3)CHO)40(CH2CH2O)26H) have been used to produce mesostructured metal sulfide films. The TMS-PLC mesophases of A-P85, B-P85 and (A + B)-P85 are well ordered with a salt/P85 mole ratio between 3.0 and 11.0 with a 3D hexagonal structure. The reaction between the mesophases of A-P85, B-P85 and ((1 - x)A + xB)-P85 and H2S gas at room temperature produces mesostructured CdS, ZnS and Cd1-xZn xS films, respectively. The initial salt concentrations in the TMS-PLC phase determine the final Cd(ii) and Zn(ii) ions in the Cd 1-xZnxS crystal structure, where x can be controlled between 0.0 and 1.0. Fresh samples of the mesophase reacted under an H 2S atmosphere are continues films that slowly leach out excess P85 producing P85 rich dendrite domains and aggregates of 50 to 100 nm particles of mesostructured CdS, ZnS or Cd1-xZnxS. However, well homogenized TMS-PLC mesophases produce stable film samples upon H2S reaction.
Open Access
The tight-binding approach to the corundum-structure d compounds
(Institute of Physics Publishing Ltd., 1994) Ivanov, V. A.
The analysis of electronic structures has been carried out for the transition-metal compounds showing the corundum-type crystal symmetry using the suggested tight-binding method for interacting bands. With the self-consistent field approximation, the branches of the electronic spectra and energy gaps have been analytically calculated. The role of the electron correlations was found to be decisive for the dielectrization of spectra for which no additional assumptions, e.g. the existence of spin- or charge-density waves, was necessary. The data obtained provide an explanation for the appearance of the insulator state in such compounds as Ti2O3, V2O 3, Cr2O3, alpha -Mn2O3 and alpha -Fe2O3. The calculated values of band gaps agree reasonably with the experimental data available. The Peierls problem is solved for the corundum-structure d compounds.