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C N R Rao

Publications and source records attributed to C N R Rao.

At least 19 recordsLinked to original sources
PubMed2007

Lamellar and three-dimensional hybrid compounds formed by cyclohexene- and cyclohexanedicarboxylates of Pb, La, and Cd.

To establish factors that determine the formation of three-dimensional hybrid structures of metal dicarboxylates involving metal-oxygen-metal linkages, we have investigated metal dicarboxylates derived from 1,2-cyclohexene as well as 1,2-, 1,3-, and 1,4-cyclohexane dicarboxylic acids. Thus, we have synthesized a 1,2-cyclohexenedicarboxylate of Cd, [Cd(1,2-CHeDC)(H2O)] (I), a 1,2-cyclohexanedicarboxylate of Pb, [Pb(1,2-CHDC)] (II), and three 1,4-cyclohexanedicarboxylates of La [La2(1,4-CHDC)3(H2O)4] (III), [La3(1,4-HCHDC)2(1,4-CHDC)5(H2O)2].H2O (IV) and [La2(1,4-CHDC)3(H2O)].2.5 H2O (V) under hydrothermal conditions and determined their structures. A mixed dicarboxylate involving both 1,3- and 1,4-cyclohexenedicarboxylates of Pb, [Pb3O(1,3-CHDC)(1,4-CHDC)].0.5 H2O (VI) and a 1,4-cyclohexanedicarboxylate of Pb, [Pb(6)O(2)(1,4-CHDC)3(1,4-HCHDC)2], have also been synthesized and characterized. While the 1,2-dicarboxylates have layered structures, the 1,4-dicarboxylates and the mixed dicarboxylates possess three-dimensional structures. Interestingly, both the 1,2 and 1,4-dicarboxylates are true hybrid compounds composed of infinite M-O-M linkages. The equatorial-equatorial (e,e) conformation is adopted commonly in all these compounds, although less stable conformations are encountered occasionally. The formation of the layered and the three-dimensional structures can be understood based on the relative disposition of the two carboxylic groups, the 1,4-isomer favoring the three-dimensional structure. Based on the results of the present study along with the available literature, we conclude that in order to obtain three-dimensional hybrid structures with metal-oxygen-metal networks, it appears necessary to make use of the 1,4-cyclohexanedicarboxylic acid.

Journal Article↗
PubMed2006

Synthesis and magnetic properties of an amine-templated Fe2+ (s = 2) sulfate with a distorted Kagome structure.

An organically templated iron(II) sulfate of the composition [H3N(CH2)2NH2(CH2)2(NH3]4[Fe(II)9F18(SO4)6].9H2O with a distorted Kagome structure has been synthesized under solvothermal conditions in the presence of diethylenetriamine. The distortion of the hexagonal bronze structure comes from the presence of two different types of connectivity between the FeF4O2 octahedra and the sulfate tetrahedra. This compound exhibits magnetic properties different from those of an Fe(II) compound with a perfect Kagome structure and is a canted antiferromagnet at low temperatures.

Journal Article↗
PubMed2006

Use of fluorous chemistry in the solubilization and phase transfer of nanocrystals, nanorods, and nanotubes.

Fluorous chemistry, involving the use of a fluorous label for the functionalization of a substrate and a fluorous solvent for extraction of the functionalized substrate, is shown to be effective in solubilizing gold and CdSe nanoparticles in a fluorous medium, through phase transfer from an aqueous or a hydrocarbon medium. While these nanoparticles were functionalized with a fluorous thiol, single-walled carbon nanotubes and ZnO nanorods could be solubilized in a fluorous medium by reacting them with a fluorous amine. Fluorous chemistry enables the solubilization of the nanostructures in the most nonpolar liquid medium possible.

Letter↗
PubMed2006

Electronic phase separation in correlated oxides: the phenomenon, its present status and future prospects.

Many transition metal oxide materials of high chemical purity are not necessarily monophasic. Thus, single crystals of chemically pure rare earth manganites and cobaltates of the general formula Ln(1-x)A(x)MO(3) (Ln=rare earth metal, A=alkaline earth metal, M=Mn, Co) exhibit the phenomenon of electronic phase separation wherein "phases" of different electronic and magnetic properties coexist. Such phase separation, the length scale of which can vary anywhere between a few nanometers to microns, gives distinct signatures in X-ray and neutron diffraction patterns, electrical and magnetic properties, as well as in NMR and other spectroscopies. While the probe one employs to investigate electronic phase separation depends on the length scale, it is noteworthy that direct imaging of the inhomogeneities has been accomplished. Some understanding of this phenomenon has been possible on the basis of some of the theoretical models, but we are far from unraveling the varied aspects of this new phenomenon. Herein, we present the highlights of experimental techniques and theoretical approaches, and comment on the future outlook for this fascinating phenomenon.

Journal Article↗
PubMed2006

Diverse structures and dimensionalities in hybrid frameworks of strontium and lanthanum with isomeric dihydroxybenzoates.

Investigations of Sr and La derivatives of 2,3-, 2,4-, 3,5-, and 2,6-dihydroxybenzoic acids have revealed that it is possible to obtain chain and layered structures of these materials. [Sr2(2,3-DHB)4(H2O)4].3H2O, I, and [Sr(2,4-DHB)2(H2O)4].H2O, II, are both one-dimensional coordination polymers based on dimers; both the carboxylate and phenolic oxygens bond to the metal in I and only the carboxylate oxygens bond to the metal in II. [Sr(3,5-DHB)2(H2O)2].4H2O, III, has a one-dimensional chain structure with large channels and involves extended Sr-O-Sr connectivity. [Sr(CH3CO2)(2,4-DHB)(H2O)3].H2O, IV, also has a chain structure with extended Sr-O-Sr connectivity, but the chain structure is formed by bridging acetate units, unlike in III where the Dihydroxybenzoate (DHB) is the bridging unit. [Sr(2,6-DHB)2(H2O)2].0.5H2O, V, is a two-dimensional coordination polymer where both carboxylate and phenolic oxygens coordinate to the metal. A lanthanum compound with the composition [La(CH3CO2)2(2,4-DHB)H2O].0.18H2O, VI, with a one-dimensional chain structure with extended La-O-La connectivity, has been prepared. Besides these chain and layered structures, zero-dimensional dimers of rare-earth DHBs with the general formula [La(CH3CO2)2(DHB)(H2O)2], with 3,5- (VII), 2,6- (VIII), and 2,3-dihydroxybenzoic acids (IX) have been synthesized. The diverse structures of the strontium and lanthanum DHBs are described. The study demonstrates that it is possible to obtain interesting structures of metal DHBs with different dimensionalities. The structures appear to be controlled largely by geometrical rather than electronic factors.

Journal Article↗
PubMed2006

The possibility of a liquid superconductor.

All superconductors are solids in their superconducting state, this canonical electronic state of matter presently having only been observed well below the melting temperature of the solid. The discovery of high-temperature superconductivity in cuprates has widened significantly our horizons of the theoretical understanding of the physical phenomenon. A number of observations point to the possibility that superconductors with a high superconducting transition temperature may not be conventional Bardeen-Cooper-Schrieffer (BCS) superconductors, but rather derive from the Bose-Einstein condensation of real-space pairs. While BCS superconductors exist in the solid state (probably with the exception of metallic liquid hydrogen at ultrahigh pressures), we argue here that a superconducting charged Bose liquid may be found in a true liquid state of condensed matter at ambient pressure. An experimental scenario is outlined in fluid metal-ammonia solutions for stabilizing and observing a high-temperature superconducting liquid (ca. 230 K) or at least a vitreous superconductor in the corresponding quenched solutions (ca. 160 K).

Journal Article↗
PubMed2006

Nanocrystalline films of Au-Ag, Au-Cu, and Au-Ag-Cu alloys formed at the organic-aqueous interface.

By the reaction of the appropriate organometallic precursors and tetrakishydroxymethyl phosphonium chloride (THPC) at the toluene-water interface, we have prepared nanocrystalline films of Au-Ag and Au-Cu alloys with a range of compositions. The films have been characterized by X-ray diffraction, electron microscopy, optical spectroscopy, and other techniques, besides compositional analysis. The particle size of the nanocrystals in the films varies with the composition. The surface plasmon band of the alloy films as well as of the organosols obtained by the disintegration of the films by the addition of an alkanethiol show the expected composition dependence. It has been possible to prepare the nanocrystalline films of a ternary Au-Ag-Cu alloy.

Journal Article↗
PubMed2006

Organically-templated metal sulfates, selenites and selenates.

The literature on inorganic open-framework materials abounds in the synthesis and characterization of metal silicates, phosphates and carboxylates. Most of these materials have an organic amine as the template. In the last few years, it has been shown that anions such as sulfate, selenite and selenate can also be employed to obtain organically templated open-framework materials. This tutorial review provides an up-to-date survey of organically templated metal sulfates, selenites and selenates, prepared under hydrothermal conditions. The discussion includes one-, two-, and three-dimensional structures of these materials, many of which possess open architectures. The article should be useful to practitioners of inorganic and materials chemistry, besides students and teachers. The article serves to demonstrate how most oxy-anions can be used to build complex structures with metal-oxygen polyhedra.

Journal Article↗
PubMed2006

Metallic ReO3 nanoparticles.

ReO3 nanoparticles in the diameter range of 8.5-32.5 nm have been prepared by decomposition of the Re2O7-dioxane complex under solvothermal conditions and characterized by X-ray diffraction, electron microscopy, optical spectroscopy, and scanning probe microscopy. The nanoparticles have the cubic (Pm3m {221} space group) structure with the lattice parameter increasing with decreasing size. The particles are metallic and show a plasmon band around 520 nm, which becomes blue-shifted with a decrease in size. The metallicity of the nanoparticles is also confirmed by tunneling conductance measurements. The nanoparticles show paramagnetic or diamagnetic behavior depending on the size, with evidence for superparamagnetism at low temperatures when the size is small.

Journal Article↗
PubMed2005

Role of the spin magnitude of the magnetic ion in determining the frustration and low-temperature properties of kagome lattices.

In view of the variety of low-temperature magnetic properties reported recently for kagome lattices with transition-metal ions in different oxidation states, we have investigated the low-energy spectrum and low-temperature thermodynamic properties of antiferromagnetic kagome lattices with varying magnitudes of site spins, employing quantum many-body Heisenberg models. The ground state and the low-lying excitation spectrum are found to depend strongly on the nature of the spin magnitude of the magnetic ions. The system remains highly frustrated if spins are half-odd-integer in magnitude, while the frustration is very weak or almost absent for integer spins or mixed-spin systems. In fact, for a mixed-spin kagome system with a certain magnitude, the whole system behaves as a classical magnet with a ferrimagnetic ground state without any frustration. These theoretical findings are consistent with a few experimental observations recently reported in the literature and would be of value in designing new kagome systems with unusual and interesting low-temperature magnetic properties.

Journal Article↗
PubMed2005

Hydrogen bonding patterns in the cocrystals of 5-nitrouracil with several donor and acceptor molecules.

: Cocrystals of 5-nitrouracil with solvent molecules, dioxane, pyridine, DMSO, formamide and ethanol as well as with piperazine, N, N'-dimethylpiperazine, 3-aminopyridine and diazabicyclo [2.2.2]octane obtained by deliberate inclusion, have been examined by X-ray crystallography. The tape structure found in the parent centric form of nitrouracil is retained with some modifications in the cocrystals with dioxane, piperazine, diazabicyclo [2.2.2]octane, N,N'-dimethylpiperazine, pyridine and DMSO, with the guest molecules forming alternate tapes. In cocrystals involving formamide, ethanol and 3-aminopyridine, the molecular tapes exhibit mixed compositions. The observed bonding patterns have been classified into six schemes. Interestingly, quadruple type hydrogen bonding patterns are seen in cocrystals containing 3-aminopyridine or ethanol and water, while a network of acyclic tetrahedral pentamers of water is found in the cocrystal containing diazabicyclo [2.2.2]octane and water.

Journal Article↗
PubMed2005

1, 2-, 1, 3- and 1, 4-Cyclohexanedicarboxylates of Cd and Mn with chain and layered structures.

A systematic study has been carried out on the three isomeric cyclohexanedicarboxylates (CHDCs) formed by cadmium and manganese with the three isomeric dicarboxylic acids, in the presence or absence of amines. The CHDCs have been prepared under hydrothermal conditions and their structures established by X-ray crystallography. We have been able to isolate two-dimensional layered structures of 1,2-, 1,3- and 1,4-cyclohexanedicarboxylates and chain structures of 1,3- and 1,4-cyclohexanedicarboxylates. The infinite metal-oxygen-metal linkages are observed only in the case of the 1,2-dicarboxylate. In all the three isomeric cyclohexanedicarboxylates, the e,e conformation is most favored, although the 1,4-CHDCs often contain rings in both the e,e and the a,e conformations.

Journal Article↗
PubMed2005

Metal aminocarboxylate coordination polymers with chain and layered structures.

The synthesis and structures of metal aminocarboxylates prepared in acidic, neutral, or alkaline media have been explored with the purpose of isolating coordination polymers with linear chain and two-dimensional layered structures. Metal glycinates of the formulae [CoCl2(H2O)2(CO2CH2NH3)] (I), [MnCl2(CO2CH2NH3)2] (II), and [Cd3Cl6(CO2CH2NH3)4] (III) with one-dimensional chain structures have been obtained by the reaction of the metal salts with glycine in an acidic medium under hydro/solvothermal conditions. These chain compounds contain glycine in the zwitterionic form. 4-Aminobutyric acid transforms to a cyclic amide under such reaction conditions, and the amide forms a chain compound of the formula [CdBr2(C4H7NO)2] (IV). Glycine in the zwitterionic form also forms a two-dimensional layered compound of the formula [Mn(H2O)2(CO2CH2NH3)2]Br2 (V). 6-Aminocaproic acid under alkaline conditions forms layered compounds with metals at room temperature, the metal being coordinated both by the amino nitrogen and the carboxyl oxygen atoms. Of the two layered compounds [Cd{CO2(CH2)5NH2}2]2 H2O (VI) and [Cu{CO2(CH2)5NH2}2]2 H2O (VII), the latter has voids in which water molecules reside.

Journal Article↗
PubMed2005

Use of the liquid-liquid interface for generating ultrathin nanocrystalline films of metals, chalcogenides, and oxides.

The air-water interface has traditionally been employed to prepare particle assemblies and films of metals and semiconductors. The interface between water and an organic liquid, however, has not been investigated sufficiently for possible use in preparing nanocrystals and thin films of materials. In this article, we demonstrate the use of the liquid-liquid interface as a medium for preparing ultrathin films of metals, chalcogenides and oxides. The method involves the reaction at the interface between a metal-organic compound in the organic layer and an appropriate reagent for reduction, sulfidation, etc. in the aqueous layer. Some of the materials discussed are nanocrystalline films of gold, CuS, CuSe, CuO, and Cu(OH)2 formed at the liquid-liquid interface. The results reported in this article should demonstrate the versatility and potential of the liquid-liquid interface for preparing nanomaterials and ultrathin films and encourage further research in this area.

Chalcogens↗