Effect of molecular association and reactivity on substitution in chromium(III)-salprn complexes

A new chromium(III)-Schiff base complex, [Cr(5-chlorosalprn)(H2O)(2)]ClO4, where salprn=N,N'-propylenebis(salicylideneimine) has been prepared and characterized by electrospray ionization mass spectrometric (ESIMS) analysis and other spectroscopic techniques. Single crystal X-ray data reveal that the complex assumes a trans-diaquo structure, [Cr(C17H18Cl2N2O4)]ClO4.H2O. The effect of phenyl ring substituents on the rate of formation of [O=Cr-V Schiff base](+) has been investigated. The bimolecular rate constant for the formation of O=Cr-V species by the [Cr(Schiff base)(H2O)(2)]ClO4, where the Schiff base=salprn, (1) and 5-chlorosalprn, (2) with PhOI was compared. In the case of (2) the rate was found to be faster by an order of magnitude at pH=4 compared to (1). The introduction of a chloro-substituent on the phenyl ring not only influences the rate of redox reactivity but also the pKa values of aquo ligands of the complexes, indicating the difference in the electronic environment around the metal ion in both (1) and (2).

Hydrothermal synthesis and structure of organically templated one-dimensional and three-dimensional iron fluorophosphate

Two new open-framework iron fluorophosphates, [C(4)N(2)H(12)](0.5) [FeF(HPO(4))(H(2)PO(4))] (I) and [C(4)N(2)H(12)][Fe(4)F(2)(H(2)O)(4)(PO(4))(4)]. 0.5H(2)O (II), were synthesized hydrothermally using piperazine as a templating agent. The structures were determined by single-crystal X-ray diffraction. Compound I crystallizes in the orthorhombic space group Pbca, a = 7.2126(2) Angstrom, b = 14.2071(4) Angstrom, c = 17.1338(2) Angstrom, Z = 8. The structure is composed of infinite anionic chains of [FeF(HPO(4))(H(2)PO(4))](n)(-) built by trans-fluorine sharing FeF(2)O(4) octahedra. These chains are similar to those found in tancoite-type minerals. Compound II crystallizes in the monoclinic space group P2(1)/n, a = 9.9045(3) Angstrom, b = 12.3011(3) Angstrom, c = 17.3220(4) Angstrom, beta = 103.7010(10)degrees, Z = 4. The structure of compound II has a three-dimensional (3D) architecture with an eight-membered channel along the b axis, in which protonoted piperazine molecules reside. The complex framework is built from two types of secondary building unit (SBU): one hexamer [Fe(3)F(2)(H(2)O)(2)(PO(4))(3)] (SBU6), and one dimer [FeO(4)(H(2)O)(2)PO(4)] (SBU2). The vertex sharing between these SBUs create the 3D structure.

New transparent crystallized glasses with optical nonlinear LiBGeO4 crystals

Crystallization behaviors of the glass with a composition of 25Li(2)O.25B(2)O(3).50GeO(2) corresponding to lithium borogermanate LiBGeO4 have been examined. It has been confirmed that the LiBGeO4 crystalline phase is formed at the surface of heat-treated glasses. The second harmonic (SH) generation is found from transparent surface crystallized glasses, demonstrating for the first time that the LiBGeO4 phase shows optical nonlinearity. The SH intensity of LiBGeO4 crystallites (powdered state) prepared through crystallization is about ten times as large as that of pulverized alpha-quartz. The SH intensity of transparent crystallized glasses (bulk state) with crystalline layers of 3-4.5 mum thickness increases with increasing heat treatment temperature (540-560degreesC) and time (1-6 h), and the maximum SH intensity among the samples studied is in the order of 1/10 in comparison with that of alpha-quartz single crystal. The transparent crystallized glass obtained by heat treatment at 550alphaC for 3 h exhibits a clear and fine Maker fringe pattern, indicating a highly orientation of LiBGeO4 crystals at the surface.

Phase transformation and semiconductor-metal transition in thin films of VO2 deposited by low-pressure metalorganic chemical vapor deposition

Thin films of the semiconducting, monoclinic vanadium dioxide, VO2(M) have been prepared on ordinary glass by two methods: directly by low-pressure metalorganic chemical vapor deposition (MOCVD), and by argon-annealing films of the VO2(B) phase deposited by MOCVD. The composition and microstructure of the films have been examined by x-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Films made predominantly of either the B or the M phase, as deposited, can only be obtained over a narrow range of deposition temperatures. At the lower end of this temperature range, the as-deposited films are strongly oriented, although the substrate is glass. This can be understood from the drive to minimize surface energy. Films of the B phase have a platelet morphology, which leads to an unusual microstructure at the lower-deposition temperatures. Those grown at similar to370 degreesC convert to the metallic, rutile (R) phase when annealed at 550 degreesC, whereas those deposited at 420 degreesC transform to the R phase only at 580 degreesC. (When cooled to room temperature, the annealed films convert reversibly from the R phase to the M phase.) Electron microscopy shows that annealing leads to disintegration of the single crystalline VO2(B) platelets into small crystallites of VO2(R), although the platelet morphology is retained. When the annealing temperature is relatively low, these crystallites are nanometer sized. At a higher-annealing temperature, the transformation leads to well-connected and similarly oriented large grains of VO2(R), enveloped in the original platelet. The semiconductor-metal transition near 68 degreesC leads to a large jump in resistivity in all the VO2(M) films, nearly as large as in epitaxial films on single-crystal substrates. When the annealed films contain well-connected large grains, the transition is very sharp. Even when preferred orientation is present, the transition is not as sharp in as-deposited VO2(M), because the crystallites are not densely packed as in annealed VO2(B). However, the high degree of orientation in these films leads to a narrow temperature hysteresis. (C) 2002 American Institute of Physics.

Synthesis and structure of La14V6CuO36.5: a transparent Cu(I) vanadate containing [OCuO](3-) sticks

The title compound, La14V6CuO36.5, was prepared from a stoichiometric mixture of La2O3,V2O5, and CuO at 1050-1080 degreesC. The compound forms transparent, pale green crystals and was characterized by wavelength dispersive spectroscopy and single crystal X-ray diffraction. The structure contains isolated VO43- tetrahedra and [OCuO](3-) sticks dispersed in a lanthanum oxide network. Films of La14V6CuO36.5 were grown on R-plane sapphire by using pulsed laser deposition. Rutherford backscattering spectroscopic and X-ray diffraction analyses of the films showed oriented growth of the title phase, a similar to5 eV optical band gap and n-type conductivity. The compound is an example of a transparent copper(I) oxide.

A Layered Zinc Phosphate, [C6N4H22][Zn6(PO4)4(HPO4)2], Formed by One-Dimensional Tubes

An open-framework zinc phosphate, [C6N4H22][Zn6(PO4)4(HPO4)2] (I), with alternating inorganic and organic layers has been synthesized hydrothermally from a starting mixture of ZnO, HCl, H3PO4, H2C2O4, and triethylenetetramine. Single-crystal data for I: monoclinic, space GROUP =P21/c (No. 14), a=9.881(1), b=16.857(1), c=8.286(1) Å, β=96.7(1)°, V=1370.8(1) Å3, Z=2, R1=0.06, and wR2=0.13 [1408 observed reflections with I>2σ(I)]. The structure of I comprises a network of ZnO4, PO4, and PO3(OH) tetrahedra forming one-dimensional tubes. The tubes, in turn, are linked via oxygen atoms forming macroanionic inorganic layers with eight-membered apertures. The one-dimensional tube-like architecture in I is a novel feature worthy of note.

Twisted aromatics, 9-anthryl and 1-pyrenyl terpyridines organize into novel multi-directional 'ladder-like' motifs in the solid state

9-Anthryl and 1-pyrenyl terpyridines (1 and 2, respectively), key precursors for the design of novel fluorescent sensors have been synthesized and characterized by H-1 NMR, mass spectroscopy and X-ray crystallography. Twisted molecular conformations for each 1 and 2 were observed in their single crystal structures. Energy minimization calculations for the 1 and 2 using the semi-empirical AM1 method show that the 'twisted' conformation is intrinsic to these systems. We observe interconnected networks of edge-to-face CH...pi interactions, which appear to be cooperative in nature, in each of the crystal structures. The two twisted molecules, although having differently shaped polyaromatic hydrocarbon substituents, show similar patterns of edge-to-face CH...pi interactions.The presently described systems comprise of two aromatic surfaces that are almost orthogonal to each other. This twisted or orthogonal nature of the molecules leads to the formation of interesting multi-directional ladder like supramolecular organizations. A combination of edge-to-face and face-to-face packing modes helps to stabilize these motifs. The ladder like architecture in 1 is helical in nature. (C) 2002 Published by Elsevier Science B.V.

A facile regioselective construction of spiro epoxy-bridged tetrahydropyranone frameworks

Investigations on the reactivity profile of the transient five-membered-ring cyclic carbonyl ylides, generated from alpha-diazo ketones, in the presence of the C=O group of various simple ketones and symrnetrical/unsymmetrical 1,2-diones were carried out. The reaction of alpha-diazo ketones with 1,2-naphthoquinone furnished interesting diastereomeric cycloadducts in which both the C=O groups acted as dipolarophilic sites. The similar reaction in the presence of several isatin derivatives afforded novel spiro dioxa-bridged indole derivatives as a mixture of diastereomers. The single crystal X-ray structure analysis manifestly revealed the mode of cycloaddition and the stereochemistry of two of the diastereomers. A diverse set of novel spiro epoxy-bridged tetrahydropyranone frameworks have been constructed in good yield via the tandem cyclization-cycloaddition of alpha-diazo ketones with the C=O group as heterodipolarophile in a regioselective manner. (C) 2003 Elsevier Ltd. All rights reserved.

An open-framework cobalt oxalato-squarate containing a ligated amine

A cobalt oxalato-squarate of the formula [Co-2(C4O4)(C2O4)(C3N2H4)(2)], containing a ligated amine has been synthesized hydrothermally and its structure determined by single crystal X-ray diffraction. The compound crystallizes in the orthorhombic space group P2(1)2(1)2 with a = 18.3845(8) Angstrom, b = 5.7884(3) Angstrom, c = 7.2598(4) Angstrom, V = 772.56(7)Angstrom(3) and Z = 4. It has a layered structure where two-dimensional sheets are formed by the connectivity of the squarate and the oxalate units with the cobalt centres, with the ligating amine molecules protruding out from the layers. (C) 2003 Editions scientifiques et medicales Elsevier SAS. All rights reserved.

Critical properties of the double-exchange ferromagnet Nd(0.6)Pb(0.4)MnO(3)

Results of a study of dc magnetization M(T,H), performed on a Nd(0.6)Pb(0.4)MnO(3) single crystal in the temperature range around T(C) (Curie temperature) which embraces the supposed critical region \epsilon\=\T-T(C)\/T(C)less than or equal to0.05 are reported. The magnetic data analyzed in the critical region using the Kouvel-Fisher method give the values for the T(C)=156.47+/-0.06 K and the critical exponents beta=0.374+/-0.006 (from the temperature dependence of magnetization) and gamma=1.329+/-0.003 (from the temperature dependence of initial susceptibility). The critical isotherm M(T(C),H) gives delta=4.54+/-0.10. Thus the scaling law gamma+beta=deltabeta is fulfilled. The critical exponents obey the single scaling equation of state M(H,epsilon)=epsilon(beta)f(+/-)(H/epsilon(beta+gamma)), where f(+) for T>T(C) and f(-) for T

Microstructural evolution in laser-ablation-deposited Fe–25 at.% Ge thin film

Films with Fe–25 at.% Ge composition are deposited by the process of laser ablation on single crystal NaCl and Cu substrates at room temperature. Both the vapor and liquid droplets generated in this process are quenched on the substrate. The microstructures of the embedded droplets show size as well as composition dependence. The hierarchy of phase evolution from amorphous to body-centered cubic (bcc) to DO3 has been observed as a function of size. Some of the medium-sized droplets also show direct formation of ordered DO19 phase from the starting liquid. The evolution of disordered bcc structure in some of the droplets indicates disorder trapping during liquid to solid transformation. The microstructural evolution is analyzed on the basis of heat transfer mechanisms and continuous growth model in the solidifying droplets.

A General Route to Nanoparticle Thin Films and Coatings

Nanoparticles thin films have wide range of applications such as nanoelectronics, magnetic storage devices, SERS substrate fabrication, optical grating and antireflective coating. Present work describes a method to prepare large area nanoparticles thin film of the order of few square centimeters. Thin film deposition has been done successfully on a wide range of conducting as well as non conducting substrates such as carbon-coated copper grid, silicon, m-plane of alumina, glass and (100) plane of NaCl single crystal. SEM, TEM and AFM studies have been done for microstructural characterization of the thin films. A basic mechanism has been proposed towards the understanding of the deposition process.

A scanning tunneling microscopy and potentiometry study of epitaxial thin films of La0.7Ca0.3MnO3

To investigate the role of grain boundaries and other growth related microstructure in manganite films, a scanning tunneling microscope is used to simultaneously probe surface topography and local potential distribution under current flow at nanometer level in films of epitaxial thin films of La0.7Ca0.3MnO3 deposited on single crystal SrTiO3 and NdGaO3 substrate by laser ablation. We have studied two types of films strained and strain relaxed. Thin (50nm) films (strained due to lattice mismatch between substrate and the film) show step growth (unit cell steps) and have very smooth surfaces. Relatively thicker films (strain relaxed, thickness 200nm) do not have these step growths and show rather smooth well connected grains. Charge transport in these films is not uniform on the nanometer level and is accompanied by potential jumps at the internal surfaces. In particular scattering from grain boundaries results in large variations in the local potential resulting in fields as high as 104-105V/cm located near the grain boundaries. We discuss the role of local strain and strain inhomogeneties in determining the current transport in these films and their resistance and magnetoresistivity. In this paper we attempt to correlate between bulk electronic properties with microscopic electronic conduction using scanning tunneling microscopy and scanning tunneling potentiometry.

Cyclometalated complexes derived from calix[4] arene bisphosphites and their catalytic applications in cross-coupling reactions

Palladium and platinum dichloride complexes of a series of symmetrically and unsymmetrically substituted 25,26;27,28-dibridged p-tert-butyl-calix[4]arene bisphosphites in which two proximal phenolic oxygen atoms of p-tert-butyl-or p-H-calix[4]arene are connected to a P(OR) ( R = substituted phenyl) moiety have been synthesized. The palladium dichloride complexes of calix[4]arene bisphosphites bearing sterically bulky aryl substituents undergo cyclometalation by C-C or C-H bond scission. An example of cycloplatinated complex is also reported. The complexes have been characterized by NMR spectroscopic and single crystal X-ray diffraction studies. During crystallization of the palladium dichloride complex of a symmetrically substituted calix[4]arene bisphosphite in dichloromethane, insertion of oxygen occurs into the Pd-P bond to give a P,O-coordinated palladium dichloride complex. The calix[4]arene framework in these bisphosphites and their metal complexes adopt distorted cone conformation; the cone conformation is more flattened in the metal complexes than in the free calix[4]arene bisphosphites. Some of these cyclometalated complexes proved to be active catalysts for Heck and Suzuki C-C cross-coupling reactions but, on an average, the yields are only modest. (C) 2011 Elsevier B.V. All rights reserved.

Magnetic order of the hexagonal rare-earth manganite Dy(0.5)Y(0.5)MnO(3)

Hexagonal Dy(0.5)Y(0.5)MnO(3), a multiferroic rare-earth manganite with geometrically frustrated antiferromagnetism, has been investigated with single-crystal neutron diffraction measurements. Below 3.4 K magnetic order is observed on both the Mn (antiferromagnetic) and Dy (ferrimagnetic) sublattices that is identical to that of undiluted hexagonal DyMnO(3) at low temperature. The Mn moments undergo a spin reorientation transition between 3.4 K and 10 K, with antiferromagnetic order of the Mn sublattice persisting up to 70 K; the antiferromagnetic order in this phase is distinct from that observed in undiluted (h) DyMnO(3), yielding a qualitatively new phase diagram not seen in other hexagonal rare-earth manganites. A magnetic field applied parallel to the crystallographic c axis will drive a transition from the antiferromagnetic phase into the low-temperature ferrimagnetic phase with little hysteresis.