Delamination of Surfactant-Intercalated Brucite-Like Hydroxy Salts of Cobalt and Copper and Solvothermal Decomposition of the Resultant Colloidal Dispersions

Surfactant anion intercalated hydroxy salts of copper and cobalt of the formula M(OH)(2-x)(surf)(x)center dot mH(2)O [M = Cu, Co; surf = dodecyl sulfate. dodecyl benzene sulfonate. and x = 0.5 for Cu and 0.67 for Co] delaminate readily in 1-butanol to give translucent colloidal dispersions that are stable for months. The extent of delamination and the colloidal dispersion observed in these solids is higher than what had been observed for layered double hydroxides. The dispersions yield the corresponding nanoparticulate oxides on solvothermal decomposition. While the copper hydroxy salt forms similar to 300 nm dendrimer-like CuO nanostructures comprising nanorods of similar to 10 nm diameter, the cobalt analogue forms similar to 20 nm superparamagnetic particles of Co3O4.

Bismuth carboxylates with Brucite- and Fluorite-related structures: synthesis structure and properties

Three new compounds of bismuth, C4N2H10]center dotBi(C7H4NO4)(C7H3NO4)]center dot H2O, I, Bi(C5H3N2O4) (C5H2N2O4)], II, and Bi(mu(2)-OH)(C7H3NO4)], III, have been prepared by the reaction between bismuth nitrate and heterocyclic aromatic dicarboxylic acids, 2,6-pyridinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, and 3,4-pyridinedicarboxylic acid, respectively, under hydrothermal conditions. The structures of all the compounds have linkages between Bi2O2 and the corresponding dicarboxylate forming a simple molecular unit in I, a bilayer arrangement in II, and a three-dimensional extended structure in III. The topological arrangement of the nodal building units in the structures indicates that a brucite-related layer (II) and fluorite-related arrangement (III) can be realized in these structures. By utilizing the secondary interactions, one can correlate the structure of III to a Kagome-related one. The observation of such classical inorganic related structures in the bismuth carboxylates is noteworthy. Lewis acid catalytic studies on the formation of ketal suggest the possible participatory role of the lone pair of electrons. All the compounds are characterized employing elemental analysis, IR, UV-vis, and thermal studies.

Stepwise Crystallization: Illustrative Examples of the Use of Metalloligands Cu-6(mna)(6)](6-) and (Ag-6(Hmna)(2)(mna)(4)](4-) (H(2)mna=2-Mercapto Nicotinic Acid) in the Formation of Heterometallic Two- and Three-Dimensional Assemblies with brucite, pcu, and sql Topologies

Three new inorganic coordination polymers, {Mn(H2O)(6)]-Mn-2(H2O)(6)](Cu-6(mna)(6)]center dot 6H(2)O}, 1, {Mn-4(OH)(2)(H2O)(10)] (Cu-6(mna)6]center dot 8H(2)O}, 2, and {Mn-2(H2O)(5)]Ag-6(Hmna)(2)(mna)(4)]center dot 20H(2)O}, 3, have been synthesized at room temperature through a sequential crystallization route. In addition, we have also prepared and characterized the molecular precursor Cu-6(Hmna)(6)]. Compounds 1 and 3 have a two-dimensional structure, whereas 2 has a three-dimensional structure. The formation of 2 has been achieved by minor modification in the synthetic composition, suggesting the subtle relationship between the reactant composition and the structure. The hexanudear copper and silver duster cores have Cu center dot center dot center dot Cu and Ag center dot center dot center dot Ag distances close to the sum of the van der Waals radii of Cu1+ and Ag1+, respectively. The connectivity between Cu-6(mna)(6)](6-) cluster units and Mn2+ ions gives rise to a brucite related layer in 1 and a pcu-net in 2. The Ag-6(Hmna)(2)(mna)(4)](4-) cluster in 3, on the other hand, forms a sql-net with Mn2+. Compound 1 exhibits an interesting and reversible hydrochromic behavior, changing from pale yellow to red, on heating at 70 degrees C or treatment under a vacuum. Electron paramagnetic resonance studies indicate no change in the valence states, suggesting the color change could be due to changes in the coordination environment only. The magnetic studies indicate weak antiferromagnetic behavior. Proton conductivity studies indicate moderate proton migrations in 1 and 3. The present study dearly establishes sequential crystallization as an important pathway for the synthesis of heterometallic coordination polymers.

Magnetic behaviour in metal-organic frameworks-Some recent examples

The article describes the synthesis, structure and magnetic investigations of a series of metal-organic framework compounds formed with Mn+2 and Ni+2 ions. The structures, determined using the single crystal X-ray diffraction, indicated that the structures possess two- and three-dimensional structures with magnetically active dimers, tetramers, chains, two-dimensional layers connected by polycarboxylic acids. These compounds provide good examples for the investigations of magnetic behaviour. Magnetic studies have been carried out using SQUID magnetometer in the range of 2-300 K and the behaviour indicates a predominant anti-ferromagnetic interactions, which appears to differ based on the M-O-C-O-M and/or the M-O-M (M = metal ions) linkages. Thus, compounds with carboxylate (Mn-O-C-O-Mn) connected ones, [C3N2H [Mn(H2O)''C6H3(COO)(3)''], I, [''Mn(H2O (3)''aEuroeC(12)H(8)O(COO)(2)'']center dot H2O, II, [''Mn(H2O)''aEuroeC(12)H(8)O(COO)(2)''], III, show simple anti-ferromagnetic behaviour. The compounds with Mn-O/OH-Mn connected dimer and tetramer units in [NaMn''C6H3(COO)(3)''], IV, [Mn-2(A mu(3)-OH) (H2O)(2)''C6H3(COO)(3)'']center dot 2H(2)O, V, show canted-antiferromagnetic and anti-ferromagnetic behaviour, respectively. The presence of infinite one-dimensional -Ni-OH-Ni- chains in the compound, [Ni-2(H2O)(A mu(3)-OH)(2)(C8H5NO4], VI, gives rise to ferromagnet-like behaviour at low temperatures. The compounds, [Mn-3''C6H3(COO)(3)''(2)], VII and [''Mn(OH)''(2)''C12H8O(COO)(2)''], VIII, have two-dimensional infinite -Mn-O/OH-Mn- layers with triangular magnetic lattices, which resemble the Kagome and brucite-like layer. The magnetic studies indicated canted-antiferromagnetic behaviour in both the cases. Variable temperature EPR and theoretical magnetic modelling studies have been carried out on selected compounds to probe the nature of the magnetic species and their interactions with them.

Organic Additive-Mediated Synthesis of Novel Cobalt(II) Hydroxides

Electrochemical precipitation of cobalt(II) hydroxide from nitrate solutions containing organic molecules, such as glucose, fructose, lactose, glycerol, and citric acid, yields a new modification of cobalt (II) hydroxide (a = 3.09 +/- 0.03 Angstrom, c = 23.34 +/- 0.36 Angstrom) that is isostructural with cu-nickel hydroxide; precipitation in the absence of organic additives gives the stable, brucite-like, beta-CO (OH)(2). (C) 1995 Academic Press, Inc.

Charge-transfer-driven inclusion of neutral TCNQ molecules in the galleries of a layered double hydroxide: an experimental and computational study

The layered double hydroxides (LDH) or anionic clays are an important class of ion-exchange materials. They consist of positively charged brucite-like inorganic sheets with charge-compensating exchangeable anions in the interlamellar space. Here we show how neutral TCNQ (7,7,8,8-tetracyanoquinodimethane) molecules can be included within the galleries of an LDH. To do so, we exploit the fact that TCNQ is a good electron acceptor that forms donor acceptor complexes with a variety of donors. The electron donor aniline was intercalated into a Mg-Al LDH as p-aminobenzoate (AB) ions by a conventional ion-exchange reaction. We show here that neutral TCNQ molecules may be driven into the galleries of the layered solid by charge-transfer complex formation with the intercalated p-aminobenzoate anions. We use diffraction and spectroscopic measurements in combination with molecular dynamics simulations and quantum chemical calculations to establish the nature of interactions and arrangement of the charge-transfer complex within the galleries of the layered double hydroxide. Electrostatic interactions between the TCNQ molecules and the anchored AB ions, subsequent to charge transfer, are the driving force for the inclusion of TCNQ molecules in the galleries of the LDH.