Example of highly stereoregulated ruthenium amidine complex formation: synthesis,crystal structures,and spectral and redox properties of the complexes [Ru(II)(trpy)[NC(5)H(4)-CH=N-N(C(6)H(5))C(CH(3))=NH]](ClO(4))(2) (1) and [Ru(II)(trpy)(NC(5)H(4)-CH=N-NH-C(6)H(5))Cl]ClO(4) (2) (trpy = 2,2':6',2"-terpyridine)

The reaction of Ru(trpy)Cl(3) (trpy = 2,2':6',2"-terpyridine) with the pyridine-based imine function N(p)C(5)H(4)-CH=N(i)-NH-C(6)H(5) (L), incorporating an NH spacer between the imine nitrogen (N(i)) and the pendant phenyl ring, in ethanol medium followed by chromatographic work up on a neutral alumina column using CH(3)CN/CH(2)Cl(2) (1:4) as eluent, results in complexes of the types [Ru(trpy)(L')](ClO(4))(2) (1) and [Ru(trpy)(L)Cl]ClO(4) (2). Although the identity of the free ligand (L) has been retained in complex 2, the preformed imine-based potentially bidentate ligand (L) has been selectively transformed into a new class of unusual imine-amidine-based tridentate ligand, N(p)C(5)H(4)-CH=N(i)-N(C(6)H(5))C(CH(3))=N(a)H (L'), in 1. The single-crystal X-ray structures of the free ligand (L) and both complexes 1 and 2 have been determined. In 2, the sixth coordination site, that is, the Cl(-) function, is cis to the pyridine nitrogen (N(p)) of L which in turn places the NH spacer away from the Ru-Cl bond, whereas, in 1, the corresponding sixth position, that is, the Ru-N(a) (amidine) bond, is trans to the pyridine nitrogen (N(p)) of L'. The trans configuration of N(a) with respect to the N(p) of L' in 1 provides the basis for the selective L --> L' transformation in 1. The complexes exhibit strong Ru(II) --> pi* (trpy) MLCT transitions in the visible region and intraligand transitions in the UV region. The lowest energy MLCT band at 510 nm for 2 has been substantially blue-shifted to 478 nm in the case of 1. The reversible Ru(III)-Ru(II) couples for 1 and 2 have been observed at 0.80 and 0.59 V versus SCE, respectively. The complexes are weakly luminescent at 77 K, exhibiting emissions at lambda(max), 598 nm [quantum yield (Phi) = 0.43 x 10(-2)] and 574 nm (Phi = 0.28 x 10(-2)) for 1 and 2, respectively.     

Stepwise synthesis of [Ru(trpy)(L)(X)](n+) (trpy = 2,2':6',2' '-terpyridine; L = 2,2'-dipyridylamine; X = Cl-, H2O, NO2-, NO+, O2-). Crystal structure, spectral, electron-transfer, and photophysical aspects

Ruthenium-terpyridine complexes incorporating a 2,2'-dipyridylamine ancillary ligand [Ru(II)(trpy)(L)(X)](ClO(4))(n) [trpy = 2,2':6',2' '-terpyridine; L = 2,2'-dipyridylamine; and X = Cl(-), n = 1 (1); X = H(2)O, n = 2 (2); X = NO(2)(-), n = 1 (3); X = NO(+), n = 3 (4)] were synthesized in a stepwise manner starting from Ru(III)(trpy)(Cl)(3). The single-crystal X-ray structures of all of the four members (1-4) were determined. The Ru(III)/Ru(II) couple of 1 and 3 appeared at 0.64 and 0.88 V versus the saturated calomel electrode in acetonitrile. The aqua complex 2 exhibited a metal-based couple at 0.48 V in water, and the potential increased linearly with the decrease in pH. The electron-proton content of the redox process over the pH range of 6.8-1.0 was calculated to be a 2e(-)/1H(+) process. However, the chemical oxidation of 2 by an aq Ce(IV) solution in 1 N H(2)SO(4) led to the direct formation of corresponding oxo species [Ru(IV)(trpy)(L)(O)](2+) via the concerted 2e(-)/2H(+) oxidation process. The two successive reductions of the coordinated nitrosyl function of 4 appeared at +0.34 and -0.34 V corresponding to Ru(II)-NO(+) --> Ru(II)-NO* and Ru(II)-NO* --> Ru(II)-NO(-), respectively. The one-electron-reduced Ru(II)-NO* species exhibited a free-radical electron paramagnetic resonance signal at g = 1.990 with nitrogen hyperfine structures at 77 K. The NO stretching frequency of 4 (1945 cm(-1)) was shifted to 1830 cm(-1) in the case of [Ru(II)(trpy)(L)(NO*)](2+). In aqueous solution, the nitrosyl complex 4 slowly transformed to the nitro derivative 3 with the pseudo-first-order rate constant of k(298)/s(-1) = 1.7 x 10(-4). The chloro complex 1 exhibited a dual luminescence at 650 and 715 nm with excited-state lifetimes of 6 and 1 micros, respectively.     

Two-wave-mixing dynamics and nonlinear hot-electron transport in transverse-geometry photorefractive quantum wells studied by moving gratings

The photorefractive response to an applied electric field is measured in a photorefractive quantum well, providing evidence in favor of the nonlinear transport in the device due to the hot electrons. The reduced mobility of the hot electrons limits the drift length, and thereby limits fringe overshoot. Thus the nonlinear transport prevents the slowing down of the grating writing rate for increasing fields which is common in bulk photorefractives. The photorefractive phase shift in transverse-field photorefractive quantum wells is measured as a function of the frequency offset between two laser writing beams that generate moving gratings. The two-wave mixing passes through a maximum at an optimum frequency which depends on the magnitude and the sign of the applied dc electric field. The phase shift associated with the moving grating adds or subtracts from the static phase shift induced by hot-electron transport in the semiconductor quantum wells, depending on the sign of the field and the sign of the dominant photocarriers. We observe a linear relationship between the roll-off frequency and the power of the writing beams. Received: 26 November 1998 / Revised version: 22 January 1999 / Published online: 12 April 1999     

Liquid-liquid extraction of 99Mo and 187W with trioctylamine

Molybdenum and tungsten can be separated from each other by extraction with trioctylamine in hydrochloric acid medium.     

Matrix-Based Analytical Model of Critical Coupling Length of Titanium In-Diffused Integrated-Optic Directional Coupler on Lithium Niobate Substrate

The critical coupling length Lc is the most important design parameter of an integrated-optic directional coupler, which is the basic building block of a variety of optical integrated circuits. The existing methods of estimating Lc of a Ti in-diffused waveguide directional coupler on LiNbO3 substrate are based on the beam propaga tion method (BPM), which requires huge computing time. A considerably simpler and computationally faster analytical method involving only multiplication of 2 x 2 matrices with no iterations is described in this article. A staircase type step-index profile is generated from the one-dimensional effective index profile in the lateral direction by partitioning the latter into a large number of thin sections of different refractive indices. The overall transfer matrix of the step-index layered structure so obtained may be computed by the progressive multiplication of individual transfer matrices (2 x 2) relating the field components in adjacent layers. Hence the wave amplitude in any layer may be computed as a function of the input wave amplitude for different angles of incidence. This method has been successfully employed to compute the propagation constants for symmetric and asymmetric guided modes in the coupled region of the directional coupler and hence compute the coupling length. The values of Lc computed for a variety of devices agree closely with the published experimental results reported by several research groups. The computer program implementing the model runs reasonably fast in an ordinary PC and is versatile enough to consider arbitrary waveguide dimensions. Ti film thickness, and diffusion parameters for any wavelength of input light and for both transverse electric and transverse magnetic polarizations.     

Discrete breathers: exact solutions in piecewise linear models

Exact breather solutions are constructed in piecewise linear (PWL) versions of the discrete nonlinear Schrodinger and Klein-Gordon equations. These solutions correspond to intersections of stable and unstable manifolds of relevant fixed points in associated 2D mappings, an exact construction of which is possible due to the PWL nature of the models. Such exact solutions give us insight into several aspects of breather properties. The problem of dynamical stability of the breathers is mentioned as an instance, detailed results on which will be presented in a future paper.     

The effect of particle size distribution on TG

The effect of a particle size distribution on the fractional reaction has been analysed. The analysis shows that for non-isothermal TG the activation energy and frequency factor evaluated from the fractional reaction by conventional method depend on the particle size distribution, and this may lead to a kinetic compensating effect. Particle size distribution may also lead to an erroneous conclusion about the change in the mechanism of reaction.     

A Simple Proof of Suzumura's Extension Theorem for Finite Domains With Applications

In this paper we provide a simple proof of the extension theorem for partial orderings due to Suzumura [1983] when the domain of the partial order is finite. The extension theorem due to Szpilrajn [1930] follows from this theorem. Szpilrajns extension theorem is used to show that an asymmetric binary relation is contained in the asymmetric part of a linear order if and only if it is acyclic. This theorem is then applied to prove three results. Finally we introduce the concept of a threshold choice function, and our third result says that such choice functions are the only ones to satisfy a property called functional acyclicity.     

Simple and Efficient Ruthenium‐Catalyzed Oxidation of Primary Alcohols with Molecular Oxygen

Oxidative transformations utilizing molecular oxygen (O₂) as the stoichiometric oxidant are of paramount importance in organic synthesis from ecological and economical perspectives. Alcohol oxidation reactions that employ O₂ are scarce in homogeneous catalysis and the efficacy of such systems has been constrained by limited substrate scope (most involve secondary alcohol oxidation) or practical factors, such as the need for an excess of base or an additive. Catalytic systems employing O₂ as the “primary” oxidant, in the absence of any additive, are rare. A solution to this longstanding issue is offered by the development of an efficient ruthenium‐catalyzed oxidation protocol, which enables smooth oxidation of a wide variety of primary, as well as secondary benzylic, allylic, heterocyclic, and aliphatic, alcohols with molecular oxygen as the primary oxidant and without any base or hydrogen‐ or electron‐transfer agents. Most importantly, a high degree of selectivity during alcohol oxidation has been predicted for complex settings. Preliminary mechanistic studies including ¹⁸O labeling established the in situ formation of an oxo–ruthenium intermediate as the active catalytic species in the cycle and involvement of a two‐electron hydride transfer in the rate‐limiting step.